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AU2003200515B2 - Viscosity drift control in overbased detergents - Google Patents
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AU2003200515B2 - Viscosity drift control in overbased detergents - Google Patents

Viscosity drift control in overbased detergents Download PDF

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Publication number
AU2003200515B2
AU2003200515B2 AU2003200515A AU2003200515A AU2003200515B2 AU 2003200515 B2 AU2003200515 B2 AU 2003200515B2 AU 2003200515 A AU2003200515 A AU 2003200515A AU 2003200515 A AU2003200515 A AU 2003200515A AU 2003200515 B2 AU2003200515 B2 AU 2003200515B2
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Australia
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combination
cst
detergent
viscosity
agent
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AU2003200515A1 (en
Inventor
Theo I Eliades
Leonard Mathews
Ronald J Muir
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General Electric Co
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General Electric Co
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Priority claimed from AU33123/99A external-priority patent/AU3312399A/en
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Description

P/00/011 Regulation 3.2
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT
ORIGINAL
TO BE COMPLETED BY APPLICANT Name of Applicant: CROMPTON CORPORATION Actual Inventors: MUIR, Ronald MATHEWS, Leonard; ELIADES, Theo I Address for Service: CALLINAN LAWRIE, 711 High Street, Kew, Victoria 3101, Australia Invention Title: VISCOSITY DRIFT CONTROL IN OVERBASED
DETERGENTS
The following statement is a full description of this invention, including the best method of performing it known to us:- 17/02/03,gc1321 I.spe,14 VISCOSITY DRIFT CONTROL IN OVERBASED DETERGENTS BACKGROUND OF THE INVENTION Field of the Invention This invention relates to viscosity drift control in overbased detergents.
Background and Discussion of the Prior Art Overbased detergents are extensively used in lubricating oils. Generally, the overbased detergent is shipped and stored prior to incorporation in the lubricating oil. The storage and shipping conditions often expose the detergent to temperatures substantially above ambient for long periods of time. It was found that some overbased detergents would, over time, and under elevated temperatures, increase in viscosity. This viscosity increase or drift caused the overbased detergent to be out of specification with the initially specified viscosity, and in certain cases the viscosity of the stored overbased detergent had suffciently increased so as not to be suitable for blending and use in the lubricating oil. The lubricating oil art was directed away from overbased detergents having high viscosity because of handling and filterability problems, as discussed in U.S. 5,011,618 to Papke et al and U.S. 4,387,033 to Lenack et al.
Overbased calcium sulfonate detergents were generally required to have a viscosity of no more than about 200 to 250 cSt at 100*C, but after several weeks of storage under elevated temperatures, the viscosity would drift to 400 cSt at 100 0 C or more. The increased or high viscosity overbased calcium sulfonate was then unsuitable for blending and use in lubricating oils.
The overbased detergent an desired a viscosity drift control agent or system.
While it was known in the lubricating oil an to add certain alkyl phenols and vegetable oils to finished blended lubricating oils to enhance certain performance characteristics, it was not known that limited amounts of such additives when added to an overbased detergent per se effectively controlled viscosity drift in long term storage prior to blending the detergent in a finished lubricating oil.
The term "viscosity drift" as used hereinbefore and hereinafter means the change (increase) in viscosity over time. The term "viscosity drift control" as used hereinbefore and hereinafter means the reduction in the change (increase) in viscosity over time.
SUMMARY OF THE INVENTION The invention provides, in one form, in combination, an overbased detergent to subject to viscosity drift, said overbased detergent selected from the group consisting of Group I and Group II metal sulfonates, phenates and carboxylates; and a viscosity drift control agent for the detergent, said viscosity drift control agent consists essentially of at least one selected from an alkyl phenol, a vegetable oil and a carboxylic acid comprising an oleophilic group and further comprising secondary hydroxyl functionality, said agent being present in an additive amount of about 0.1 to 5.0% by weight, whereby the detergent with the agent over time in storage prior to incorporation in a lubricating oil, the detergent viscosity drift is reduced.
A viscosity drift control system for overbased detergents is achieved by the addition of additive amounts of a compound having an oleophilic group and having secondary hydroxyl functionality. This viscosity drift control additive or agent when added in additive amounts to the overbased detergent results in a viscosity which over several weeks at elevated temperatures remains relatively unchanged or slightly elevated, whereas absent the agent, the viscosity would over time increase to a commercially unacceptable degree. The agent of the present invention permits the overbased product to remain in specification.
The viscosity drift control agent is effective in amounts of 0.1 to 5% by weight and preferably 0.25 to 1.0% by weight in the overbased detergent. These additive amounts of the viscosity drift control agent reduce the viscosity drift to less than a 10% increase in the initial viscosity over a period of 4 weeks at elevated temperatures above about 35 0
C.
The viscosity control agent generally includes vegetable oils, carboxylic acids, and alkyl phenols.
02/1203,at 1321 I.specipgs,2 DESCRIPTION OF THE PREFERRED EMBODIMENTS' In one broad aspect, the viscosity drift control agents of the present invention include compounds having both an oleophilic group and secondary hydroxyl functionality. It is to be understood that such secondary hydroxyl functionality pursuant to the present invention contemplates OH, OH-HO hydrogen bonding as in inter-fatty acid triglyceride hydrogen bonding vegetable oils) and OH in the ester form of this functional group. The control agents or compounds are preferably of moderately high molecular weight The viscosity drift control agent has a molecular weight of about 150 to 1,000 or more, and as a practical matter, preferably between 280 and 1,000.
It has been found that generally three classes of compounds fall within the aforesaid definition of viscosity drift control agents pursuant to the present invention. These classes of viscosity drift control agents include vegetable oils, carboxylic acids and alkyl phenols, having an oleophilic group and further having secondary hydroxyl functionality. Suitable vegetable oils include canola oil, jojoba oil, sunflower oil, rapeseed oil, linseed oil, palm kernel oil and the like. Vegetable oils such as canola oil and jojoba oil are preferred. The alkyl phenols include mono, di, linear and branched alkyl phenols. The alkyl group of the alkyl phenol may have up to 40 carbon atoms, and preferably 6 to 20 carbon atoms. Useful alkyl phenols are heptyl phenols, octylphenols, dodecylphenols, nonylphenols and cyclohexyl phenols. It is to be understood that the terms "alkyl phenol" or "alkyl phenols" are used herein to represent one or more such alkyl phenols. Dinonyl phenol is a preferred alkyl phenol. Suitable carboxylic acids pursuant to the present invention include capric, lauric, mvristic, palmitic, stearic, isosteanc, arachidic, behenic, lignoceric, lauroleic, myristoleic, palmitoleic, oleic, gadoleic, erucic, ricinoleic, linoleic and linoleic acids. A 12-hydroxy stearic acid a preferred carboxylic acid. It is to be noted that the aforesaid useful compounds contain an oleophilic group and also contain secondary hydroxyl functionality.
The control agent is effective in amounts of 0.1 to 5°/o by weight and preferably 0.25 to The viscosity drift control effect is proportional to the amount of agent added to the detergent. The viscosity drift effected by additive amounts of the control agents of the present invention is less than about 10% over 4 weeks. That is, the initial viscosity of the combination of the overbased detergent and control agent increases or drifts less than about 10% over 4 weeks.
The controlled viscosity drift is about 5 to 25 cSt at 100'C, where 0.1 to 5% by weight of the control agent is added to the overbased detergent and the detergent stored at about 46* C to 490 C for four weeks.
It has been generally found that detergents stored for about 4 weeks, particularly at elevated temperatures of above about 35 C, had viscosity drifts of at least about 30% or more.
Where control agents of the present invention are added to the detergent in additive amounts of 0.1 to 5% by weight, the viscosity drift is generally -educed to about 10% to 15% over 4 weeks at such elevated temperatures. In certain cases, the viscosity control agents of the present invention reduced the viscosity drift to less than about 10% over 4 weeks at elevated temperatures above about 350 C.
It has been found that one of the most preferred and most effective viscosity drift control agents is an alkyl phenol, and particularly dinonyl phenol (DNP). It was found and as further demonstrated herein that about 0.5% by weight of DNP in a detergent reduced the viscosity drift to less than about 10% where the detergent was stored at elevated temperatures of about 370 C 4to 820 C for about 4 weeks. The lubricating oil art is particularly conservative in that it is reluctant to introduce new compounds into commercial lubricating oils. The alkyl phenols are particularly preferred because they bear structural similarity to phenates, which in one form are commercially useful overbased detergents. The use of an alkyl phenol, such as dinonyl phenol, is then perceived by the lubricating oil art as not introducing a structurally suspect compound in the lubricating oil blend which might result in adverse performance characteristics. Further, insofar as only 0.5% by weight of DNP is extremely effective, DNP is most preferred for its minimal use requirement and concomitant low cost, as well as for its structural acceptability.
The foregoing viscosity drift control agents are produced by procedures well know in the an and are commercially available. Canola oil is a particularly effective agent, and is readily commercially available and inexpensive, and for these reasons is another preferred viscosity drift control agent.
The overbased detergents products are produced by procedures well known in the an and are commercially available. Suitable detergents useful in the present inventions include the Group I and Group I metal sulfonates, phenates and carboxylates. Particularly useful for viscosity drift control are the overbased calcium sulfonate and phenates. Highly overbased sulfonates and phenates are particularly subject to increased viscosity, and the drift control agents of the present invention are particularly effective for these highly overbased products. Highly overbased sulfonates and phenates are those having a TBN in excess of about 200 and preferably more than 400.
Examples 1-3 A sample of an overbased calcium sulfonate, TBN 400, was produced by sulfonating a 310 to 700 SUS at 100°F petroleum oil and blending with 0 to 30% sulfonic acid made by sulfonating a synthetic, mainly dialkyl benzene alkylate having'a molecular weight of 430 to 560.
The sulfonic acid composition is overbased by carbonating in the presence of calcium hydroxide, solvent, alcohol and oil, according to procedures well known in the art. The product calcium sulfonate had an initial viscosity of 331 cSt at 100 0 C and was treated with dinonyl phenol (Example canola.oil (Example 2) and jojoba oil (Example 3) and held at about 46° C to about 49° C for several weeks during which time the viscosities were measured.
Example 1 Dinonyl phenol Viscosities cSt 100" C Amt. added Initial 1 wk 2 wks 3 wks 4 wks 0 331 cSt 377 cSt 402 cSt 424 cSt 446 cSt 0.25 275 cSt 280 cSt 289 cSt 294 cSt 300 cSt 0.50 257 cSt 262 cSt 268 cSt 276 cSt 280 cSt 1.00 238 cSt 245 cSt 250 cSt 256 cSt 259 cSt 2 226 cSt 231 cSt 236 cSt 241 cSt 246 cSt 3 210 cSt 210 cSt 212 cSt 214 cSt 216 cSt Examnile 2 Canola Oil Viscosities cSt (b 1000 C Amnt. added Initial I wk 2 wks wks 4 wks 0.50 255 cSt 262 cSt 273 cSt 285 cSt 311 cSt 1.00 237 cSt 242 cSt 1249 cSt 255 cSt 261 cSt 2 212 cSt 213 cSt 217 cSt 222 cSt 227 ct 166 cSt 166 cSt 167 cSt 178 cSt 170OcSt Example 3 Jojoba Oil Viscosities cSt a.h 1000 C Amnt. added Initial Ilwk 2 wks 3 wks 4 wks 5.00 142 cSt 147 cSt l 50OcSt 154 cSt 155SCst The results of Examples 1-3 demonstrate that dinonyl phenol and the vegetable oils, canola and jojoba oils, provide significant viscosity drift control under elevated temperatures of 460 C to 490 C over an extended period of 4 weeks. The viscosity drift using 0.2 to 5% of the control agent dinonyl phenol, canola oil and jojoba oil), after four weeks under elevated temperatures of about 460 C to about 490 C, is no more than about 5 to 25 cSt at 100TC.
Examples I and 2 further demonstrate that the viscosity drift control is proportional to the amount of agent added.
ExaMple 4 An overbased calcium suLfonate having a 405 TBN was stored at 71 *C to 820 C with diverse control agents added, and the viscosity was measured over several weeks.
Additive Viscosity cSt 100 0
C
Amount initial I wk 2 wks 3 wks 4 wks none 268 289 320 360 405 dinonviphenol 1254 255 266 272 279 dinonvlohenol 235 245 246 253 257 dinonvlphenol 12-33 231 236 243 246 canola oil [170 180 180 187 193 12-hydroxy 266 261 274 288 295 steaxic joioba oil 170 180 180 187 192 ioioba oil 167 171 174 177 178 The results of Example 4 demonstrate that diverse viscosity drift control agents within the scope of the invention effectively reduce viscosityv drift to no more than about 10% for detergents stored for 4 weeks at elevated temperatures of 710' C to 820 C.
Example Controls An overbased calcium sulfonate having a 405 TBN was stored at 710 C to 82° C blended with additive amounts of diverse compounds not within the scope or definition of the invention, and the viscosity measured over several weeks.
Additive Viscosity cSt 100 0
C
Amount (wt. initial I wk 2 wks 3 wks 4 wks none 268 289 320 360 405 2% water 230 265 310 355 402 2% Co-530 220 265 297 330 385 (ethoxvlated phenol) 1% Rhodamine T 226 242 280 320 362 Example 5 demonstrates that diverse compounds outside the scope of the definition of the present invention are not useful as viscosity drift control agents.
Example 6 Dinonyl Phenol (DNP) The following Tables 6A and 6B (viscosity vs. temperature) report the viscosities of an overbased calcium sulfonate having a 400 TBN, with and without dinonyl phenol (DNP), respectively, where in both cases the detergent was stored for 4 weeks at the same specified temperatures.
-9- Table 6A. 400 TBN Overbased Calcium SuLfonate Without DNP Viscosities cSt 100' C Temperature 37.*O C 49.9 0 C 65i.60 C 82.20 C initial 193 cSt 193 cSt i 93 cSt 193 cSt 1 wk 194 cSt 203 cSt 207 cSt 209 cSt 2 wks 196 cSt 201 cSt 216 cSt 216 cSt 3 wks 203 cSt 220 cSt 232 cSt 236 cSt 4 wks 207 cSt 228 cSt 251 cSt 265 cSt Table 6B. Same 400 TBN Overbased Calcium Suifonate wiNth 0.5%o DNP Viscosities cSt 1000 C Temperature 37.80 C 48.9 0 C 65.60 C 82.2 0 C initial 181 cSt 181 cSt 181 cSt 181 cSt 1 wk 4l83 cSt 186 cSt 184 cSt 188 cSt 2 wks 178 c~t 182 cSt 186 cSt 189 cSt 3 wks 181 cSt 186 cSt 191 cSt 195 cSt S wk'~ 187 cSt 189 cSt I13 cSt 1 20 1 c.-)t 4_ 1 The results of Tables 6A and 6B clearly demonstrate that with the use of a 0.5% DNP drift control agent, the viscosity readings of a 400 TBN calcium sulfonate deterg-ent were relatively stable over four weeks, even at the elevated temperatures at which the tests were conducted. More specifically, where the overbased calcium sulfonate detergent was stored at temperatures of from about 370 C to 820 C for 4 weeks, with 0.5% DNP and without DNP, it was further demonstrated that the DNP controlled viscosity drift to less than about While the invention is demonstrated for certain alkyl phenols,-vegetable oils and carboxylic acids, it is to be understood that all such compounds having an oleophilic group and also having secondary hydroxyl functionality are with the contemplation of the invention.
Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.
11-

Claims (14)

1. In combination, an overbased detergent subject to viscosity drift, said overbased detergent selected from the group consisting of Group I and Group II metal sulfonates, phenates and carboxylates; and a viscosity drift control agent for the detergent, said viscosity drift control agent consists essentially of at least one selected from an alkyl phenol, a vegetable oil and a carboxylic acid comprising an oleophilic group and further comprising secondary hydroxyl functionality, said agent being present in an additive amount of about 0.1 to 5.0% by weight, whereby the detergent with the agent over time in storage prior to incorporation in a lubricating oil, the detergent viscosity drift is reduced. I0
2. The combination of claim 1, wherein the viscosity drift of the detergent is less than about 10% over 4 weeks.
3. The combination of claim 1 or claim 2, wherein the agent is present in an amount of 0.25 to 1.0% by weight.
4. The combination of claim 1, wherein the viscosity drift is no more than about 5 to cSt at 100 0 C with the detergent stored at about 46 0 C to about 49 0 C for about 4 weeks.
5. The combination of claim 1, wherein the detergent comprises an overbased calcium sulfonate.
6. The combination of claim 1, wherein the detergent comprises an overbased calcium phenate.
7. The combination of claim 1, wherein the agent comprises an alkyl phenol.
8. The combination of claim 7, wherein the alkyl phenol comprises dinonyl phenol.
9. The combination of claim 1, wherein the agent comprises a vegetable oil.
The combination of claim 9, wherein the vegetable oil comprises canola oil.
11. The combination of claim 9, wherein the vegetable oil comprises jojoba oil. 02/12/03,at1321 I.speipgs,2
12- I 12. The combination of claim 1, wherein the agent comprises a carboxylic acid.
13. The combination of claim 12, wherein the carboxylic acid comprises a hydroxy stearic acid.
14. The combination of claim 12, wherein the carboxylic acid comprises a monohydroxy alkane monocarboxylic acid having from 8 to 18 carbon atoms or higher. The combination as defined in any one of claims 1 to 14, substantially as hereinbefore described with reference to any one of the examples. DATED this 2 nd day of December, 2003 CROMPTON CORPORATION By their Patent Attorneys: CALLINAN LAWRIE <o^t4 A4 02/12/03,at]3211.specipgs,2 -13-
AU2003200515A 1998-02-26 2003-02-17 Viscosity drift control in overbased detergents Ceased AU2003200515B2 (en)

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US09031284 1998-02-26
AU33123/99A AU3312399A (en) 1998-02-26 1999-02-25 Viscosity drift control in overbased detergents
AU2003200515A AU2003200515B2 (en) 1998-02-26 2003-02-17 Viscosity drift control in overbased detergents

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818325A (en) * 1955-04-22 1959-08-12 Bataafsche Petroleum Process for the preparation of non-gelling solutions of oil-soluble basic salts of organic acids in oils
EP0094814A2 (en) * 1982-05-14 1983-11-23 Exxon Research And Engineering Company Lubricating oil additives
US5505867A (en) * 1994-07-06 1996-04-09 Ritter; Clyde G. Fuel and Lubrication oil additive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB818325A (en) * 1955-04-22 1959-08-12 Bataafsche Petroleum Process for the preparation of non-gelling solutions of oil-soluble basic salts of organic acids in oils
EP0094814A2 (en) * 1982-05-14 1983-11-23 Exxon Research And Engineering Company Lubricating oil additives
US5505867A (en) * 1994-07-06 1996-04-09 Ritter; Clyde G. Fuel and Lubrication oil additive

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