Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS20050124510 A1
Publication typeApplication
Application numberUS 10/731,600
Publication dateJun 9, 2005
Filing dateDec 9, 2003
Priority dateDec 9, 2003
Also published asCN1890354A, CN100482776C, EP1699910A2, WO2005061683A2, WO2005061683A3
Publication number10731600, 731600, US 2005/0124510 A1, US 2005/124510 A1, US 20050124510 A1, US 20050124510A1, US 2005124510 A1, US 2005124510A1, US-A1-20050124510, US-A1-2005124510, US2005/0124510A1, US2005/124510A1, US20050124510 A1, US20050124510A1, US2005124510 A1, US2005124510A1
InventorsMichael Costello, Igor Riff, Joseph Weaver
Original AssigneeCostello Michael T., Igor Riff, Weaver Joseph A.Jr.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Low sediment friction modifiers
US 20050124510 A1
Abstract
An additive mixture for lubricant oils includes an overbased alkaline earth metal sulfonate, and at least one friction modifier selected from the group consisting of an overbased alkaline earth carboxylate, the reaction product of an alkanolamine with a fatty acid or a fatty acid ester and the reaction product of thiodiglycol or a dialkylene glycol with a fatty acid or a fatty acid ester. The additive mixture, when combined with a lubricant stock, provides a lubricant composition characterized by less sedimentation during storage.
Images(2)
Previous page
Next page
Claims(20)
1. An additive mixture for lubricant oils which comprises:
a) an overbased alkaline earth metal sulfonate; and,
b) at least one friction modifier selected from the group consisting of a polyalkylene succinic anhydride, an overbased alkaline earth carboxylate, the reaction product of an alkanolamine with a fatty acid or a fatty ester, the reaction product of thiodiglycol with a fatty acid or a fatty ester and the reaction product of a dialkylene glycol with a fatty acid or a fatty ester.
2. The additive mixture of claim 1 wherein the overbased alkaline earth metal sulfonate is overbased calcium sulfonate.
3. The additive mixture of claim 2 wherein the overbased calcium sulfonate is an amorphous overbased calcium sulfonate having a particle size of no more than about 30 nm.
4. The additive mixture of claim 2 wherein the overbased calcium sulfonate is a crystalline overbased calcium sulfonate having a particle size of from at least about 50 nm to about 100 nm.
5. The additive mixture of claim 1 wherein the friction modifier comprises polyisobutylene succinic anhydride.
6. The additive mixture of claim 1 wherein the friction modifier comprises calcium carboxylate.
7. The additive mixture of claim 1 wherein the friction modifier comprises barium carboxylate.
8. The additive mixture of claim 1 wherein the friction modifier comprises the reaction product of triethanolamine with a fatty acid or fatty acid ester.
9. The additive mixture of claim 8 wherein the friction modifier comprises the reaction product of triethanolamine with one or more of a fatty compound selected from the group consisting of methyl oleate, tall oil fatty acid, oleic acid, ricinoleic acid, isostearic acid, erucic acid, mixed oleic acid/stearic acid and iso-oleic acid.
10. The additive mixture of claim 1 wherein the friction modifier comprises the reaction product of thiodiglycol with methyl oleate.
11. The additive mixture of claim 1 wherein the friction modifier comprises the reaction product of a diethylene glycol with methyl oleate.
12. A lubricant composition comprising:
a) a lubricant oil stock
b) an overbased alkaline earth metal sulfonate; and,
c) at least one friction modifier selected from the group consisting of a polyalkylene succinic anhydride, an overbased alkaline earth carboxylate, the reaction product of an alkanolamine with a fatty acid or a fatty ester, the reaction product of thiodiglycol with a fatty acid or a fatty ester and the reaction product of a dialkylene glycol with a fatty acid or a fatty ester.
13. The lubricant composition of claim 12 wherein the overbased alkaline earth sulfonate is an amorphous overbased calcium sulfonate having a particle size of no more than about 30 nm.
14. The lubricant composition of claim 12 wherein the overbased alkaline earth sulfonate is a crystalline overbased calcium sulfonate having a particle size of from at least about 30 nm to about 50 nm.
15. The lubricant composition of claim 12 wherein the friction modifier comprises the reaction product of triethanolamine with a fatty acid or fatty acid ester.
16. The lubricant composition of claim 15 wherein the friction modifier comprises lubricant composition.
17. The lubricant composition of claim 12 wherein the friction modifier comprises the reaction product of thiodiglycol with methyl oleate.
18. The lubricant composition of claim 12 wherein the friction modifier comprises the reaction product of diethylene glycol with methyl oleate.
19. A method for storing a lubricant composition comprising the steps of:
a) combining with a lubricant stock an additive mixture including
i) an overbased alkaline earth metal sulfonate; and,
ii) at least one friction modifier selected from the group consisting of a polyalkylene succinic anhydride, an overbased alkaline earth carboxylate, the reaction product of an alkanolamine with a fatty acid or a fatty acid ester, the reaction product of thiodiglycol with a fatty acid or a fatty ester and the reaction product of a dialkylene glycol with a fatty acid or a fatty ester, to provide a lubricant composition;
b) containing said lubricant composition within a vessel.
20. The method of claim 19 wherein said overbased alkaline earth sulfonate is overbased calcium sulfonate, and the friction modifier is selected from the group consisting of the reaction product of triethanolamine with one or more of a fatty compound selected from the group consisting of methyl oleate, tall oil fatty acid, oleic acid, isostearic acid and mixed oleic acid/stearic acid, overbased barium carboxylate, overbased calcium carboxylate and the reaction product of thiodiglycol with methyl oleate.
Description
    BACKGROUND OF THE INVENTION
  • [0001]
    1. Technical Field
  • [0002]
    The present invention relates to friction modifiers for lubricant oils used, for example, in engines for motorized vehicles.
  • [0003]
    2. Description of the Related Art
  • [0004]
    Friction modifiers for enhancing the lubricity of lubricant oils are known. Typical friction modifiers include esters of glycerol and fatty acids, overbased carboxylates, and oxidized petroleum fractions. Also known is the use of detergent additives such as overbased calcium sulfonates. However, a common problem which occurs when aging the lubricant oil is the formation of sediment.
  • [0005]
    During storage, especially under warm temperature conditions, sedimentation occurs in stocks of lubricant oils containing friction modifiers and detergent additive. In a storage tank containing many thousands of gallons of lubricant oil fluid, a sedimentation rate of a few percent can correspond to a thousand or more gallons of bottom sediment, which is clearly undesirable. What is needed is an additive for lubricant oils which provides a friction modifier and detergent, and which is characterized by a low sedimentation rate.
  • SUMMARY
  • [0006]
    An additive mixture for lubricant oils is provided herein. The additive mixture comprises: (a) an overbased alkaline earth metal sulfonate; and, (b) at least one friction modifier selected from the group consisting of an overbased alkaline earth carboxylate, the reaction product of an alkanolamine with a fatty acid or a fatty acid ester, the reaction product of thiodiglycol with a fatty acid or a fatty ester and the reaction product of a dialkylene glycol with a fatty acid or a fatty ester.
  • [0007]
    The additive mixture provides a lubricant oil composition having improved lubricity and exhibits less sedimentation.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0008]
    Various embodiments are described below with reference to the drawings wherein:
  • [0009]
    FIG. 1 is a graph illustration the sedimentation results of Example 75; and,
  • [0010]
    FIG. 2 is a graph illustrating the friction test results of Example 76.
  • DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)
  • [0011]
    Lubricating oil compositions used to lubricate the moving parts of engines, especially internal combustion engines, contain base oil of lubricating viscosity, or a mixture of such oils, and additives used to improve the performance characteristics of the oil. For example, additives are used to improve detergency, reduce engine wear, to provide stability against heat and oxidation, to reduce oil consumption, to inhibit corrosion, to act as a dispersant, and reduce friction loss. Some additives provide multiple benefits, such as a dispersant/viscosity modifier. Other additives, while improving one characteristic of the lubricating oil, have an adverse affect on other characteristics. Thus to provide a lubricating oil having optimal overall performance, it is necessary to characterize and understand all the effects of the various additives available, and carefully balance the additive content of the lubricant.
  • [0012]
    The present invention is a low sediment additive mixture for lubricant oils which comprises an overbased alkaline earth metal sulfonate with a selected friction modifier.
  • [0013]
    The additive mixture can be added to any type of lubricant oil including metal cutting and drawing oils, although motor oils are preferred. The lubricant oils can be natural or synthetic. Natural oils include petroleum oils, solvent-treated, acid treated or hydrotreated mineral oils, coal oil and shale oil. The lubricant oil can include saturated, olefinic unsaturated and aromatic components. Furthermore, the lubricant oil can include hydrocarbon and/or non-hydrocarbon components such as fatty acids and fatty acid esters.
  • [0014]
    Overbased alkaline earth sulfonates are detergent compounds prepared by neutralizing a sulfonic acid with an excess of alkaline earth metal base (e.g., the hydroxides of magnesium, calcium or barium) so as to produce an overbased alkaline earth metal sulfonate with a total base number (“TBN”) of greater than zero. The TBN is the amount of acid needed to neutralize all of the alkalinity of the overbased material, and can be determined according to ASTM D 2896. A composition with a TBN of about 100 or less is considered to be a “low overbased material.” A TBN of about 100 to 300 is characterized as “moderate overbasing.” A composition with a TBN of over 300 is considered to be a “highly overbased” material. The preferred overbased alkaline earth metal sulfonate is overbased calcium sulfonate having a TBN of above about 250, preferably above about 350, and more preferably 400 or higher.
  • [0015]
    In one aspect of the invention it has been found that amorphous overbased calcium sulfonate is superior to crystalline calcium overbased sulfonate in terms of undesired sedimentation. An amorphous overbased calcium sulfonate suitable for use in the present inventor in commercially available from Cromptom Corporation of Middlebury CT under the designation Calcinate™ C-400 CLR. The amorphous overbased calcium sulfonate has a particle size of less than about 30 nm. Crystalline overbased calcium sulfonates have a particle size above 30 nm, preferably 50-500 nm and more preferably 50-100 nm. Calcinate™ C-300CS, available from Crompton Corporation, is an example of a crystalline overbased calcium sulfonate. A method for preparing highly overbased calcium sulfonate is described in U.S. Pat. No. 6,444,625 B1, which is herein incorporated by reference.
  • [0016]
    In another aspect of the invention it has been found that certain friction modifiers, when combined with an overbased alkaline earth sulfonate, exhibit lower sedimentation properties.
  • [0017]
    The lubricant composition also comprises a friction modifier to reduce the coefficient of friction. The friction modifier and overbased calcium sulfonate can be combined and packaged with other additives such as antioxidants, dispersants and/or defoamers, or other types of additives such as mentioned above.
  • [0018]
    Various friction modifiers can be used in the additive mixture. Such friction modifiers include glycerol monoesters, overbased carboxylates, overbased tall oil fatty acids, the reaction product of an alkanolamine (e.g., triethanolamine (“TEA”) or diethanolamine) or a glycol (e.g., thiodiglycol, diethylene glycol) with a fatty acid or fatty ester, oxygenated petroleum fractions, alkoxylated alkylamine and the reaction products of glycols with fatty esters.
  • [0019]
    Glycerol monoesters useful as friction modifiers include, for example, glycerol esters of saturated or unsaturated C8 to C20 fatty acids such as glycerol monopalmitate, glycerol monostearate, glycerol monooleate, and the like.
  • [0020]
    Overbased carboxylates are known and are generally prepared by reacting an acidic material, normally an acidic gas such as SO2 or CO2, and most commonly carbon dioxide, with a mixture comprising a carboxylic acid and a stoichiometric excess of an alkaline base metal compound in a reaction medium, preferably with a promoter. The base metal is preferably an alkaline earth metal such as magnesium, calcium or barium in the form of an oxide or hydroxide. The carboxylic acid is preferably a saturated or unsaturated carboxylic acid having from about 8 to about 30 carbon atoms. Useful carboxylic acids include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, decanoic acid, dodecanoic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, 12-hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, arachidic acid, gadoleic acid, eicosadienoic acid, behenic acid, erucic acid, mixtures of any of these acids or their reactive equivalent.
  • [0021]
    Other suitable overbased carboxylates include overbased calcium tallate and overbased barium tallate.
  • [0022]
    A reaction product of TEA and fatty ester suitable for use as a friction modifier is the reaction product of TEA and methyl oleate. Other suitable friction modifiers include the reaction products of TEA with, for example, oleic acid, ricinoleic acid, isostearic acid, erucic acid, tall oil fatty acid (TOFA), mixed oleic/stearic acids, and iso-oleic acid.
  • [0023]
    Oxygenated petroleum fractions are known. Petroleum oxidates and methods for making them are disclosed in U.S. Pat. No. 5,439,602, which is herein incorporated by reference.
  • [0024]
    Also suitable for use as friction modifiers are the reaction products of thiodiglycol with fatty acids or fatty esters (e.g., oleic acid, methyl oleate, etc.), and the reaction products of a dialkylene glycol (e.g., diethylene glycol, dipropylene glycol, etc.) with a fatty acid or fatty ester (e.g., oleic acid, methyl oleate, etc.).
  • [0025]
    In another aspect of the invention it has been found that overbased alkaline earth sulfonate (especially crystalline overbased calcium sulfonate) provides a lubricant oil composition with greater lubricity (i.e., lower coefficient of friction). Particularly preferred as a friction modifier are the reaction products of TEA with fatty acids or fatty esters for both excellent lubricity and low sedimentation. A preferred crystalline overbased calcium sulfonate is available from Crompton Corp. under the designation Calcinate C300CS and has a particle size of about 50-500 nm. Preferred particle size for a crystalline overbased calcium sulfonate ranges from about 50 nm to about 100 nm.
  • [0026]
    The following Examples illustrate features of the invention. In one type of experiment, illustrated below in Examples 1-30 and 59-75, lubricant oils containing a selected overbased calcium sulfonate and a selected friction modifier were tested for sedimentation. In another type of experiment, exemplified in Examples 31-58 and 76, the lubricant oils containing combinations of selected overbased calcium sulfonates and friction modifiers were tested for friction reducing characteristics.
  • EXAMPLES 1-8
  • [0027]
    These examples are directed to a study of the sedimentation characteristics of various blends of overbased calcium sulfonate and selected friction modifiers. Two types of overbased calcium sulfonates were individually tested. Calcinate™ C300CS is a crystalline overbased calcium sulfonate having TBN of about 300 and a particle size of from about 50 nm to about 100 nm, and is available from Crompton Corporation. Calcinate™ C400CLR is an amorphous overbased calcium sulfonate available from Crompton Corporation having TBN of about 400 and a particle size of no more than about 30 nm. Overbased calcium sulfonates were present in 10% concentrations. The friction modifier included glycerol mono oleate (“GMO”). Polyisobutylene succinic anhydride (“PIBSA”) having a molecular weight of about 1,050, was present in Examples 3, 4, and 7 as a dispersant. The friction modifier was present in 1% concentrations when employed. The lubricant oil stock was a severely hydrotreated naphthenic oil available from Ergon, Inc. under the designation Hyprene H100. Hyprene H100 is characterized by an API gravity (60 F.) of 24.6, a pour point of −50 F., and an aniline point of 163 F. The respective overbased calcium sulfonate and friction modifier were combined with the diluent lubricant stock and placed in a 100 ml centrifuge tube in a 70 C. oven for a period of 12 weeks. The sediment formed was measured at one week intervals and recorded as percentages. In examples 1 and 5, no friction modifiers were employed. It can be seen that use of the amorphous overbased calcium sulfonate Calcinate C400CLR (Examples 5-8) reduces sedimentation dramatically. It is believed that the reduced sedimentation of the amorphous variety of overbased calcium sulfonate is related to its smaller particle size.
  • [0028]
    The results of theses experiments are set forth in Table 1.
  • [0029]
    The sediments formed in the Calcinate™ C300CS Examples 1 to 4 were analyzed by FTIR by removing an aliquot of sediment from the bottom layer with a pipette. In all sediments there was a strong peak at 881 cm−1, which is an indication of CaCO3 in the calcite form. There were no peaks observed from sulfonate, which did not precipitate with the calcite.
    TABLE 1
    Example
    1 2 3 4 5 6 7 8
    C300CS 10% 10% 10% 10%
    C400CLR 10% 10% 10% 10%
    PIBSA  1%  1%  1%  1%
    GMO  1%  1%  1%  1%
    Hyprene H100 90% 89% 89% 88% 90% 89% 89% 88%
    % Sediment,
    70 C. @
    Week
     1 0.01 0.35 0.55 0.35 0 0 0 0
     2 0.35 0.25 0.50 0.30 0 0 0 0
     3 0.30 0.30 0.50 0.30 0 0 0 0
     4 0.30 0.30 0.65 0.25 0 0 0 0
     5 0.25 0.25 0.50 0.30 0 0 0 0
     6 0.25 0.25 0.30 0.25 0.001 0.002 0.001 0.002
     7 0.30 0.25 0.40 0.25 0.002 0.002 0.001 0.002
     8 0.25 0.25 0.40 0.25 0.002 0.002 0.001 0.005
     9 0.25 0.25 0.35 0.25 0.002 0.002 0.002 0.005
    10 0.25 0.25 0.40 0.25 0.002 0.002 0.002 0.005
    11 0.25 0.25 0.35 0.25 0.002 0.002 0.005 0.010
    12 0.25 0.25 0.35 0.25 0.002 0.002 0.005 0.010
    Final centrifuge 0.25 0.20 0.35 0.25 0.001 0.002 0.002 0.005
  • EXAMPLES 9 to 16
  • [0030]
    Sedimentation experiments were conducted in the same manner as in Examples 1-8 except that the friction modifiers tested were an oxidized petroleum fraction available under the designation Alox 165L from Lubrizol, an overbased calcium oleate, designated herein as “OCO”, and GMO. The friction modifiers, when employed, were each present in 0.5% concentration. Examples 10 and 14 did not employ any friction modifiers.
  • [0031]
    As can been seen from the results the amorphous overbased calcium sulfonate Calcinate™ C400CLR (Examples 13-16) was characterized by very low sedimentation percentages (typically about 0.001 to about 0.005) as opposed to the sedimentation percentages (0.11 to 0.50) for the Calcinate™ C300CS (Examples 9-12).
  • [0032]
    The results of these experiments are set forth in Table 2.
    TABLE 2
    Example
    9 10 11 12 13 14 15 16
    C300CS  10%  10%  10%  10%
    C400CLR  10%  10%  10%  10%
    Alox 1652 0.5% 0.5%
    OCO 0.5% 0.5%
    GMO 0.5% 0.5%
    Hyprene H100 89.5%  90 89.5 89.5 89.5 90 89.5 89.5
    % Sediment, 70 C. @
    Week
     1 0.50 0.40 0.02 0.40 0.001 0.001 0.001 0.001
     2 0.40 0.35 0.03 0.30 0.001 0.001 0.001 0.001
     3 0.35 0.30 0.02 0.30 0.001 0.001 0.001 0.001
     4 0.35 0.30 0.05 0.30 0.001 0.001 0.001 0.001
     5 0.35 0.30 0.11 0.30 0.001 0.001 0.001 0.001
     6 0.30 0.25 0.20 0.25 0.001 0.001 0.001 0.002
     7 0.30 0.25 0.40 0.25 0.005 0.002 0.002 0.002
     8 0.30 0.25 0.20 0.25 0.005 0.005 0.002 0.005
     9 0.30 0.25 0.20 0.25 0.005 0.005 0.002 0.005
    10 0.30 0.25 0.20 0.25 0.005 0.005 0.002 0.005
    11 0.30 0.25 0.25 0.25 0.005 0.005 0.005 0.005
    12 0.30 0.25 0.25 0.25 0.005 0.005 0.005 0.005
    Final centrifuge 0.30 0.25 0.20 0.25 0.005 0.002 0.002 0.002
  • EXAMPLES 17 to 28
  • [0033]
    Sedimentation experiments were conducted in a manner similar to Examples 9 to 16, except that the friction modifiers tested were OCO (overbased calcium oleate), Alox 302 (oxygenated petroleum fraction), an overbased barium tallate having 3% -10% barium and designated herein as “OBT”, an overbased calcium tallate having 4%-10% calcium and designated herein as “OCT”, and GMO (glycerol mono oleate). Examples 22 and 28 did not employ any friction modifier.
  • [0034]
    As can be seen, the amorphous overbased calcium sulfonate Calcinate™ C400CLR (Example 23-28) is characterized by much lower percentages of sedimentation as opposed to the sedimentation percentages for the crystalline overbased calcium sulfonate Calcinate™ C300CS (Examples 17-22).
  • [0035]
    The results of these experiments are set forth in Table 3
    TABLE 3
    Example
    17 18 19 20 21 22 23 24 25 26 27 28
    C300CS  10%  10%  10%  10%  10%  10%
    C400CLR  10%  10%  10%  10%  10%  10%
    OCO 0.5% 0.5%
    Alox 302 0.5% 0.5%
    OBT 0.5% 0.5%
    OCT 0.5% 0.5%
    GMO 0.5% 0.5%
    Hyprene 89.5%  89.5 89.5 89.5 89.5 90 89.5 89.5 89.5 89.5 89.5 90
    % Sediment
    70 C. @ Week
     1 0.001 0.001 0 0 0.45 0.01 0 0 0 0 0 0
     2 0.002 0.35 0.01 0.01 0.35 0.25 0 0 0 0 0 0
     3 0.030 0.40 0.02 0.04 0.35 0.25 0 0 0.001 0.001 0.001 0.001
     4 0.030 0.35 0.05 0.05 0.30 0.25 0 0.001 0.001 0.001 0.001 0.001
     5 0.030 0.30 0.03 0.075 0.25 0.25 0.001 0.001 0.002 0.002 0.001 0.001
     6 0.030 0.40 0.04 0.10 0.25 0.25 0.001 0.001 0.001 0.001 0.001 0.001
     7 0.040 0.35 0.04 0.10 0.25 0.30 0.001 0.001 0.002 0.002 0.001 0.001
     8 0.040 0.35 0.05 0.15 0.25 0.30 0.001 0.002 0.002 0.002 0.001 0.002
     9 0.050 0.30 0.05 0.15 0.25 0.20 0.001 0.002 0.002 0.002 0.001 0.002
    10 0.050 0.30 0.05 0.15 0.25 0.25 0.001 0.002 0.002 0.002 0.001 0.002
    11 0.070 0.30 0.05 0.15 0.25 0.25 0.001 0.002 0.002 0.002 0.002 0.002
    12 0.070 0.30 0.05 0.15 0.25 0.25 0.001 0.001 0.002 0.002 0.002 0.002
  • EXAMPLES 29 to 30
  • [0036]
    Sedimentation experiments were conducted in the same manner as in the previous examples except that the friction modifiers included 0.5% of a reaction product of TEA and tall oil fatty acid resulting in a trioleate ester, which is designated herein as “TEA-T”.
  • [0037]
    The results set forth in Table 4 illustrate that the amorphous overbased calcium sulfonate Calcinate™ C400CLR was (Examples 31, 32) was characterized by much lower sedimentation percentages than the sedimentation percentages for crystalline overbased calcium sulfonate Calcinate™ C300CS. But also the use of TEA-T as a friction modifier with Calcinate™ C300CS surprisingly provided a lubricant blend with much lower sedimentation then that employing the GMO/ET-2 friction modifier.
    TABLE 4
    Example
    29 30
    C300 CS   10%
    C400 CLR   10%
    TEA-T  0.5%  0.5%
    GMO
    Hyprene H100 89.5% 89.5%
    Total % Sediment @ 70 C.
    Week:
     1 0.001 0   
     2 0.010 0.001
     3 0.020 0.001
     4 0.020 0.001
     5 0.020 0.002
     6 0.030 0.001
     7 0.040 0.002
     8 0.050 0.002
     9 0.050 0.002
    10 0.050 0.002
  • EXAMPLES 31-44
  • [0038]
    These Examples are directed to the friction reducing characteristics of the lubricant oil blends. The coefficient of friction for the selected blends was measured with a Cameron-Plint TE-77 high frequency friction test. The conditions are set forth below
    Upper specimen 6 mm 16 mm Dowel EN
    1A (BS 1804 Part 1 Grade 1, 220M07)
    Lower specimen Flat hardened ground NSOH BO1
    Gauge Plate (RC 60/0.4 μm)
    Frequency  5 Hz
    Load (N) 50-100
    Amplitude 15 mm
  • [0039]
    Temperature Profile for Cameron Plint Test
    Load Ramp Temperature Dwell
    Stage (N) Time (min) C. Time (min)
    1 0 10 35 5
    2 50 10 50 5
    3 100 60 165
  • [0040]
    In Examples 33 to 48 Calcinate™ C300CS and Calcinate™ C400CLR are compared on equal weight.
    TABLE 5
    Example
    31 32 33 34 35 36 37 38 39 40 41 42 43 44
    C300CS   10%   10%   10%   10%   10% 10%   10%
    C400CLR   10%   10%   10%   10%   10% 10%   10%
    OCO  0.5%  0.5%
    Alox 165L  0.5%  0.5%
    OBT  0.5%  0.5%
    OCT  0.5%  0.5%
    GMO  0.5%  0.5%
    Tea-T  0.5%  0.5%
    Dil Oil 89.5% 89.5% 89.5% 89.5% 89.5% 90% 89.5% 89.5% 89.5% 89.5% 89.5% 89.5% 90% 89.5%
    CoF@60 0.1250 0.1125 0.1275 0.1125 0.1000 0.1267 0.1025 0.1325 0.1090 0.1060 0.1100 0.0960 0.1390 0.1210
     70 0.1150 0.1050 0.1175 0.1060 0.0960 0.1258 0.0975 0.1375 0.1060 0.1125 0.1100 0.0910 0.1450 0.1265
     80 0.1100 0.1025 0.1100 0.1020 0.0940 0.1222 0.0950 0.1390 0.1060 0.1150 0.1100 0.0900 0.1440 0.1270
     90 0.0950 0.0950 0.1000 0.0975 0.0900 0.1160 0.0890 0.1375 0.1040 0.1060 0.1060 0.0875 0.1440 0.1270
    100 0.0875 0.0860 0.0925 0.0910 0.0860 0.1115 0.0860 0.1375 0.1020 0.0980 0.1025 0.0850 0.1425 0.1265
    110 0.0825 0.0825 0.0860 0.0890 0.0825 0.1013 0.0820 0.1375 0.1000 0.0910 0.1025 0.0840 0.1425 0.1245
    120 0.0825 0.0790 0.0825 0.0850 0.0790 0.0945 0.0740 0.1325 0.0975 0.0840 0.1000 0.0810 0.1390 0.1213
    130 0.0825 0.0775 0.0790 0.0810 0.0760 0.0908 0.0690 0.1300 0.0960 0.0760 0.0980 0.0800 0.1150 0.1163
    140 0.0850 0.0760 0.0775 0.0800 0.0760 0.0883 0.0660 0.1325 0.0940 0.0760 0.0950 0.0790 0.1075 0.1150
    150 0.0875 0.0800 0.0800 0.0790 0.0825 0.0867 0.0700 0.1340 0.0925 0.0660 0.0930 0.0775 0.1125 0.1125
    160 0.0875 0.0800 0.0825 0.0800 0.0820 0.0858 0.0720 0.1275 0.0950 0.0590 0.0900 0.0750 0.1175 0.1090
    Average 0.0945 0.0887 0.0941 0.0912 0.0858 0.1045 0.0821 0.1344 0.1002 0.0900 0.1015 0.0842 0.1317 0.1206
  • EXAMPLES 45-58
  • [0041]
    These Examples were conducted in a manner similar to those of Examples 33 to 49 except that Calcinate™ C300CS and Calcinate™ C400CLR were compared on the basis of equal TBN rather than equal weight. The results are set forth in Table 6.
    TABLE 6
    Example
    45 46 47 48 49 50 51 52 53 54 55 56 57 58
    C300CS   10%   10%   10%   10%   10% 10%   10%
    C400CLR   10%   10%   10%   10%   10% 10%   10%
    OCO  0.5%  0.5%
    Alox 165L  0.5%  0.5%
    OBT  0.5%  0.5%
    OCT  0.5%  0.5%
    GMO  0.5%  0.5%
    TEA-T  0.5%  0.5%
    Dil Oil 89.5% 89.5% 89.5% 89.5% 89.5% 90% 89.5% 89.5% 89.5% 89.5% 89.5% 89.5% 90% 89.5%
    CoF@60 0.1250 0.1125 0.1275 0.1125 0.1000 0.1267 0.1025 0.1325 0.1090 0.1060 0.1100 0.0960 0.1390 0.1210
     70 0.1150 0.1050 0.1175 0.1060 0.0960 0.1258 0.0975 0.1375 0.1060 0.1125 0.1100 0.0910 0.1450 0.1265
     80 0.1100 0.1025 0.1100 0.1020 0.0940 0.1222 0.0950 0.1390 0.1060 0.1150 0.1100 0.0900 0.1440 0.1270
     90 0.0950 0.0950 0.1000 0.0975 0.0900 0.1160 0.0890 0.1375 0.1040 0.1060 0.1060 0.0875 0.1440 0.1270
    100 0.0875 0.0860 0.0925 0.0910 0.0860 0.1115 0.0860 0.1375 0.1020 0.0980 0.1025 0.0850 0.1425 0.1265
    110 0.0825 0.0825 0.0860 0.0890 0.0825 0.1013 0.0820 0.1375 0.1000 0.0910 0.1025 0.0840 0.1425 0.1245
    120 0.0825 0.0790 0.0825 0.0850 0.0790 0.0945 0.0740 0.1325 0.0975 0.0840 0.1000 0.0810 0.1390 0.1213
    130 0.0825 0.0775 0.0790 0.0810 0.0760 0.0908 0.0690 0.1300 0.0960 0.0760 0.0980 0.0800 0.1150 0.1163
    140 0.0850 0.0760 0.0775 0.0800 0.0760 0.0883 0.0660 0.1325 0.0940 0.0760 0.0950 0.0790 0.1075 0.1150
    150 0.0875 0.0800 0.0800 0.0790 0.0825 0.0867 0.0700 0.1340 0.0925 0.0660 0.0930 0.0775 0.1125 0.1125
    160 0.0875 0.0800 0.0825 0.0800 0.0820 0.0858 0.0720 0.1275 0.0950 0.0590 0.0900 0.0750 0.1175 0.1090
    Average 0.0945 0.0887 0.0941 0.0912 0.0858 0.1045 0.0821 0.1344 0.1002 0.0900 0.1015 0.0842 0.1317 0.1206
  • EXAMPLES 59-74
  • [0042]
    A study was made of various friction modifiers to determine sedimentation at 12 weeks. The Experiments were conducted by blending crystalline overbased calcium sulfonate Calcinate C300CS (10 wt %) with Hyprene H100 lubricant oil stock, and 0.5% of the selected friction modifier. The composition was then placed in a 70 C. oven in a 100 ml centrifuge tube and the sediment formed was measured at one week intervals. The sediments formed ranged from flocculant white/gray material to black solids, although no attempts were made to separately quantify the different types observed. Rather, only the total amount of sediment observed in the centrifuge was recorded so that simple comparisons could be made. The total amount of sediments formed at the end of the 12 week period are reported in Table 7. For comparison, the blend of Calcinate C300CS plus lubricant oil but without a friction modifier was conducted to provide a baseline comparison and was recorded at 0.25%. The mixed oleic/stearic glycol is available from Arizona Chemical Co. under the designation Uniflex 1803. The friction modifiers of Examples 65-74 are the reaction products of the specified compounds.
  • [0043]
    As can be seen the use of friction modifies comprising the reaction product of TEA with methyl oleate, tall oil fatty acid, oleic acid, isostearic acid and mixed oleic/stearic acids resulted in low sedimentation as compared with the baseline level of 0.25%. Also, the use of the reaction product of thiodiglycol and methyl oleate resulted in low sedimentation. Overbased alkaline earth carboxylates also provided low sedimentation.
    TABLE 7
    Sediment
    Example Friction Modifier (12 Weeks)
    59 Glycerol mono oleate 0.25%
    60 Overbased calcium carboxylate (OCO) 0.25%
    61 Overbased barium carboxylate (OBT) 0.05%
    62 Overbased calcium carboxylate (OCT) 0.15%
    63 Oxidized petrolatum (Alox 165L) 0.30%
    64 Mixed oleic/stearic glycol (Uniflex 1803) 0.25%
    65 TEA + methyl oleate 0.05%
    66 TEA + tall oil fatty acid 0.06%
    67 TEA + oleic acid 0.05%
    68 TEA + ricinoleic acid 5.10%
    69 TEA + isostearic acid 0.15%
    70 TEA + erucic acid 0.35%
    71 TEA + mixed oleic/stearic acids 0.20%
    72 TEA + iso-oleic acid 1.10%
    73 Thiodiglycol + methyl oleate 0.20%
    74 Diethylene glycol + methyl oleate 4.20%
  • EXAMPLE 75
  • [0044]
    The sedimentation tests of Examples 59 to 74 were extended past the 12 week period to determine the nature of failure mode of separation. The results of selected friction modifiers are shown in FIG. 1. A comparison is made with friction modifier produced by the reaction of TEA with a monomeric fatty acid distillate obtained from the dimerization of tall oil fatty acid, such as a mixture of branched and straight chain fatty acids available from Arizona Chemical Co. under the designation Century™ D-1. Also shown in FIG. 1 are the sedimentation test results of a friction modifier produced by the reaction of TEA with a mixture of C18 mon-unsaturated mostly methyl branched fatty acids, available from Arizona Chemical Co. under the designation Century™ D1164.
  • [0045]
    The results show an initial induction period of very low sedimentation followed by a catastrophic failure the sediment completely precipitates in a one week period forming a distinct layer. The layer then continues to compact over the next 2-4 weeks and reduces the sediment volume, as can be seen from the TEA+ricinoleic acid, or diethylene glycol+methyl oleate tests. In a second mode the sediment layer forms more slowly after the induction period, but a flocculant material is observed in the supernatant liquid. While the sediment layer does not settle any further, the floc in the supernatant liquid appears to separate into a distinct layer which causes the level of sediment to increase over time, as can be seen from the tests involving TEA+TOFA, TEA+oleic acid, and TEA+iso-oleic acid. There does not appear to be any correlation between the failure mode and the structure of the friction modifier used. However, while not wishing to be bound to any specific theory, it is suggested that the formation of a more dense sediment would more completely separate in the catastrophic failure mode whereas a lighter precipitate would tend to flocculate and settle more slowly after failure.
  • EXAMPLE 76
  • [0046]
    Friction tests were performed on selected combinations of overbased calcium sulfonate and friction modifiers of Example 75 in accordance with the testing method set forth in Examples 31-58. The results are illustrated in FIG. 2.
  • [0047]
    It can readily be appreciated that storage of a lubricant oil composition in a vessel over an extended period of time can be accompanied by much less sedimentation by adding to a lubricant stock a mixture including an overbased alkaline earth metal sulfonate, such as overbased calcium sulfonate, and a friction modifier in accordance with the invention.
  • EXAMPLE 77
  • [0048]
    This Example illustrates the preparation of the reaction product of TEA with tall oil fatty acid.
  • [0049]
    A 250 mL 3-neck round-bottom flask equipped with an agitator, thermocouple and distallation condenser was charged with 0.062 mol triethanol amine, 0.185 tall oil fatty acid and 0.003 mol para-tolune sulfonic acid catalyst. The system was purged with nitrogen for 3-4 minutes, then the nitrogen flow was turned down to a minimum. The system was agitated and heated to 160 C. Once at this temperature, the nitrogen flow was increased to facilitate the removal of water. Conditions were held for 5 hours after which time IR analysis showed the acid carbonyl absorbance (1712 cm-1) to be absent. The reaction was cooled to 100 C. and the catalyst was neutralized with 0.70 grams of a Hitec 611 (a 300 TBN detergent). The reaction was filtered to remove solids. The product obtained, was 62 grams of light amber, low viscosity liquid.
  • EXAMPLE 78
  • [0050]
    This example illustrates the synthesis of a reaction product of diethylene glycol with methyl oleate to obtain ethylene glycol dioleate.
  • [0051]
    25 Parts of diethylene glycol and 139.7 parts of methyl oleate were combined in a 3-neck round bottom flask. The mixture was heated to 100 C. with stirring under a nitrogen sweep. At 100 C., 0.26 parts of dibutyl tin diacetate catalyst was added and the mixture was tehn heated to 180 C. After 4.33 hours the system was cooled to 100 C. and 1.1 parts of Filtrol 20 acid clay was added to neutralize the catalyst. The system was stirred for 15 minutes and the contents of the flask were then filtered with vacuum. The final product was 136.43 parts of low viscosity dark yellow fluid.
  • [0052]
    While the above description contains many specifics, these specifics should not be construed as limitations of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other embodiments within the scope and spirit of the invention as defined by the claims appended hereto.
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2454568 *Jul 14, 1945Nov 23, 1948Drew & Co Inc E FThioglycol esters
US3194761 *Mar 3, 1961Jul 13, 1965Distillers Co Yeast LtdPreparation of overbased sulphurized calcium alkylphenate lubricant additives
US3198737 *Dec 23, 1960Aug 3, 1965Shell Oil CoLubricating compositions and additives therefor
US3429811 *Aug 17, 1966Feb 25, 1969Exxon Research Engineering CoPreparation of overbased sulfonates
US3754684 *Aug 26, 1970Aug 28, 1973Elitex Z Textilniho StrojuenstCentral lubricating dispenser
US4057504 *Nov 22, 1976Nov 8, 1977Karonite Chemical Co., Ltd.Method of preparing overbased lubricating oil additives
US4123369 *Dec 1, 1976Oct 31, 1978Continental Oil CompanyLubricating oil composition
US4335004 *Jan 11, 1980Jun 15, 1982Phillips Petroleum CompanyLubricating compositions containing diesters of dimercapto ethers
US4358387 *Aug 10, 1981Nov 9, 1982Texaco Inc.Cylinder lubricating oil composition
US4375417 *Oct 27, 1981Mar 1, 1983Texaco Inc.Cylinder lubricating oil composition
US4388201 *Jul 20, 1981Jun 14, 1983Exxon Research & Engineering Co.Co-dispersant stabilized friction modifier lubricating oil composition
US4502970 *May 12, 1983Mar 5, 1985Exxon Research & Engineering Co.Lubricating oil composition
US4505829 *Oct 29, 1981Mar 19, 1985Exxon Research & Engineering Co.Lubricating oil composition containing sediment-reducing additive
US4614602 *May 1, 1985Sep 30, 1986Amoco CorporationLubricant overbased detergent-dispersants with improved solubility
US4704217 *Aug 20, 1986Nov 3, 1987Texaco Inc.Gasoline crankcase lubricant
US4938881 *Aug 1, 1988Jul 3, 1990The Lubrizol CorporationLubricating oil compositions and concentrates
US4952328 *Jun 3, 1988Aug 28, 1990The Lubrizol CorporationLubricating oil compositions
US4954273 *Oct 27, 1988Sep 4, 1990The Lubrizol CorporationOil formulations containing overbased multi-functional additive
US4995993 *Dec 18, 1989Feb 26, 1991Texaco Inc.Process for preparing overbased metal sulfonates
US5013463 *Nov 19, 1986May 7, 1991Amoco CorporationProcess for overbased petroleum oxidate
US5071576 *Oct 11, 1988Dec 10, 1991Exxon Chemical Patents Inc.Lubricant oil additive
US5112506 *Oct 11, 1988May 12, 1992Exxon Chemical Patents Inc.Overbased metal sulphonate composition
US5137648 *Jul 15, 1991Aug 11, 1992Exxon Chemical Patents Inc.Overbased metal sulphonate composition
US5250203 *Feb 12, 1992Oct 5, 1993The Lubrizol CorporationLubricating oil compositions containing a polyoxyalkylene carboxylic acid salt additive
US5283276 *Jun 25, 1990Feb 1, 1994Exxon Chemical Patents Inc.Coating compositions
US5294354 *Jun 5, 1992Mar 15, 1994Texaco Inc.Combining dispersant viscosity index improver and detergent additives for lubricants
US5314632 *Jun 5, 1992May 24, 1994Texaco Inc.Combining dispersant viscosity index improver and detergent additives for lubricants
US5318710 *Mar 12, 1993Jun 7, 1994Chevron Research And Technology CompanyLow viscosity Group II metal overbased sulfurized C16 to C22 alkylphenate compositions
US5320762 *Mar 12, 1993Jun 14, 1994Chevron Research And Technology CompanyLow viscosity Group II metal overbased sulfurized C12 to C22 alkylphenate compositions
US5320763 *Mar 12, 1993Jun 14, 1994Chevron Research And Technology CompanyLow viscosity group II metal overbased sulfurized C10 to C16 alkylphenate compositions
US5326485 *Sep 10, 1993Jul 5, 1994Ethyl Petroleum Additives, Inc.Low ash lubricating oil compositions
US5330663 *Sep 2, 1992Jul 19, 1994Chevron Research And Technology CompanyNeutral and low overbased alkylphenoxy sulfonate additive compositions
US5330664 *Sep 2, 1992Jul 19, 1994Chevron Research And Technology CompanyNeutral and low overbased alkylphenoxy sulfonate additive compositions derived from alkylphenols prepared by reacting an olefin or an alcohol with phenol in the presence of an acidic alkylation catalyst
US5330665 *Mar 18, 1985Jul 19, 1994Bp Chemicals (Additives) LimitedProduction of either an alkaline earth metal alkyl phenate or a sulphurised alkaline earth metal alkyl phenate
US5433871 *Nov 23, 1993Jul 18, 1995Bp Chemicals (Additives) LimitedProcess for the production of a lubricating oil additive concentrate
US5437803 *Jul 22, 1993Aug 1, 1995Bp Chemicals (Additives) LimitedProcess for the production of a lubricating oil additive concentrate
US5439602 *Jul 6, 1994Aug 8, 1995Witco CorporatonOverbased sulfonates combined with petroleum oxidates for metal forming
US5464548 *Aug 11, 1994Nov 7, 1995The Lubrizol CorporationLubricants, functional fluid and grease compositions containing sulfite or sulfate overbased metal salts and methods of using the same
US5490945 *Apr 28, 1994Feb 13, 1996The Lubrizol CorporationLubricating compositions and concentrates
US5562864 *Nov 3, 1994Oct 8, 1996The Lubrizol CorporationLubricating compositions and concentrates
US5602084 *May 24, 1995Feb 11, 1997Bp Chemicals (Additives) LimitedDetergent additives for lubricating oils, their preparation and use
US5614480 *Jul 25, 1994Mar 25, 1997The Lubrizol CorporationLubricating compositions and concentrates
US5652201 *Jul 11, 1995Jul 29, 1997Ethyl Petroleum Additives Inc.Lubricating oil compositions and concentrates and the use thereof
US5678466 *Mar 12, 1994Oct 21, 1997Wahl; WilfriedProcess and a device for lubricating and cooling cutting edges and/or workpieces in machining processes with chip removal, and their use in sawing machines
US5780398 *Jul 24, 1997Jul 14, 1998Chevron Chemical CompanyHigh overbased alkyloxy aromatic sulfonate-carboxylates as lube oil additives
US5804094 *Feb 27, 1996Sep 8, 1998Exxon Chemical Patents, Inc.Low base number sulphonates
US5804537 *Nov 21, 1997Sep 8, 1998Exxon Chemical Patents, Inc.Crankcase lubricant compositions and method of improving engine deposit performance
US5885943 *Dec 18, 1997Mar 23, 1999Exxon Chemical Patents Inc.Sulfur boron antiwear agents for lubricating compositions
US6034039 *Nov 25, 1998Mar 7, 2000Exxon Chemical Patents, Inc.Lubricating oil compositions
US6090760 *Dec 16, 1997Jul 18, 2000Lubrizol Adibis Holdings (Uk) Ltd.Sulphurized alkaline earth metal hydrocarbyl phenates, their production and use thereof
US6107259 *Jul 15, 1998Aug 22, 2000Witco CorporationOil soluble calcite overbased detergents and engine oils containing same
US6140279 *Apr 9, 1999Oct 31, 2000Exxon Chemical Patents IncConcentrates with high molecular weight dispersants and their preparation
US6159912 *Nov 5, 1998Dec 12, 2000Chevron Chemical Company LlcLow viscosity, chloride-free, low overbased alkyl-aryl-sulfonate, its application as an additive for lubricating oil, and methods of preparation
US6197075 *Apr 2, 1998Mar 6, 2001Crompton CorporationOverbased magnesium deposit control additive for residual fuel oils
US6204226 *Jun 3, 1999Mar 20, 2001Chevron Oronite S.A.Mixture of alkyl-phenyl-sulfonates of alkaline earth metals, its application as an additive for lubricating oil, and methods of preparation
US6239083 *Jun 2, 2000May 29, 2001Crompton CorporationClarification method for oil dispersions comprising overbased detergents containing calcite
US6239084 *Jul 21, 1999May 29, 2001Crompton CorporationViscosity drift control in overbased detergents
US6294506 *Jul 15, 1994Sep 25, 2001Chevron Chemical CompanyLubricating oils having carbonated sulfurized metal alkyl phenates and carbonated metal alkyl aryl sulfonates
US6417148 *May 16, 1997Jul 9, 2002Infineum Usa L.P.Overbased metal-containing detergents
US6429178 *May 16, 1997Aug 6, 2002Infineum Usa L.P.Calcium overbased metal-containing detergents
US6444624 *Sep 20, 2000Sep 3, 2002Juliet V. WalkerLubricating oil composition
US6444625 *Sep 6, 2000Sep 3, 2002Crompton CorporationHigh viscosity overbased sulfonate detergent and marine cylinder oils containing same
US6479440 *Jan 25, 2001Nov 12, 2002Chevron Oronite S. A.Alkaline earth alkylaryl sulfonates, their application as an additive for lubricating oil, and methods of preparation
US6569821 *Jan 3, 2000May 27, 2003Infineum Usa L.P.Overbased metal detergents
US6599867 *Jan 31, 2002Jul 29, 2003Infineum International Ltd.Overbased detergent additives
US20020137636 *Dec 19, 2001Sep 26, 2002Hartley Rolfe J.Lubricating oil composition
US20040063589 *Sep 19, 2003Apr 1, 2004Omg Americas, Inc.Lubricant compositions containing an overbased amorphous alkaline earth metal salt as a metal protectant
US20040180798 *Mar 10, 2003Sep 16, 2004Hartley Rolfe J.Friction modifiers for engine oil composition
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7422999 *Feb 14, 2005Sep 9, 2008The Lubrizol CorporationOverbased vaterite containing salt composition
US8114822 *Oct 24, 2006Feb 14, 2012Chemtura CorporationSoluble oil containing overbased sulfonate additives
US9023771Jul 27, 2006May 5, 2015Nissan Motor Co., Ltd.Nanoparticle-containing lubricating oil compositions
US20060183650 *Feb 14, 2005Aug 17, 2006The Lubrizol CorporationOverbased vaterite containing salt composition
US20080096777 *Oct 24, 2006Apr 24, 2008Costello Michael TSoluble oil containing overbased sulfonate additives
US20090018037 *Jul 27, 2006Jan 15, 2009Nissan Motor Co., Ltd.Nanoparticle-containing lubricating oil compositions
US20090048129 *Aug 7, 2008Feb 19, 2009Nissan Motor Co., Ltd.Nanoparticle-containing lubricating oil compositions
EP1980609A1 *Jul 27, 2006Oct 15, 2008Nissan Motor Co., Ltd.Nanoparticle-containing lubricating oil compositions
Classifications
U.S. Classification508/306, 508/411, 508/391, 508/413, 508/460
International ClassificationC10M163/00
Cooperative ClassificationC10M2207/26, C10M2219/046, C10M2219/084, C10N2230/06, C10N2260/04, C10M2203/1065, C10M2207/283, C10M2207/129, C10M163/00, C10M2215/042, C10M2203/10, C10N2220/082, C10M2207/123, C10M2219/085, C10M2207/289, C10N2210/02, C10N2230/52
European ClassificationC10M163/00
Legal Events
DateCodeEventDescription
Apr 5, 2004ASAssignment
Owner name: CROMPTON CORPORATION, CONNECTICUT
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COSTELLO, MICHAEL T.;RIFF, IGOR;WEAVER, JOSEPH A.;REEL/FRAME:015180/0608
Effective date: 20040105
May 15, 2008ASAssignment
Owner name: CHEMTURA CORPORATION, CONNECTICUT
Free format text: CHANGE OF NAME;ASSIGNOR:CROMPTON CORPORATION;REEL/FRAME:020960/0562
Effective date: 20050701
Aug 27, 2009ASAssignment
Owner name: CHEMTURA CORPORATION, CONNECTICUT
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOEY, MICHAEL DENNIS;REEL/FRAME:023158/0755
Effective date: 20080725
Feb 22, 2010ASAssignment
Owner name: CITIBANK, N.A.,DELAWARE
Free format text: AMENDED AND RESTATED INTELLECTUAL PROPERTY SECURITY AGREEMENT;ASSIGNORS:CHEMTURA CORPORATION;A & M CLEANING PRODUCTS, LLC;AQUA CLEAR INDUSTRIES, LLC;AND OTHERS;REEL/FRAME:023998/0001
Effective date: 20100212
Owner name: CITIBANK, N.A., DELAWARE
Free format text: AMENDED AND RESTATED INTELLECTUAL PROPERTY SECURITY AGREEMENT;ASSIGNORS:CHEMTURA CORPORATION;A & M CLEANING PRODUCTS, LLC;AQUA CLEAR INDUSTRIES, LLC;AND OTHERS;REEL/FRAME:023998/0001
Effective date: 20100212
Mar 21, 2011ASAssignment
Owner name: BIOLAB FRANCHISE COMPANY, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: HOMECARE LABS, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: WEBER CITY ROAD LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: MONOCHEM, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: ISCI, INC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: NAUGATUCK TREATMENT COMPANY, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: UNIROYAL CHEMICAL COMPANY LIMITED (DELAWARE), CONN
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: ASEPSIS, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: CHEMTURA CORPORATION, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: WRL OF INDIANA, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: CROMPTON COLORS INCORPORATED, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: LAUREL INDUSTRIES HOLDINGS, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: RECREATIONAL WATER PRODUCTS, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: GLCC LAUREL, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: GT SEED TREATMENT, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: CROMPTON MONOCHEM, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: KEM MANUFACTURING CORPORATION, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: GREAT LAKES CHEMICAL GLOBAL, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: A & M CLEANING PRODUCTS, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: GREAT LAKES CHEMICAL CORPORATION, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: CROMPTON HOLDING CORPORATION, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: ASCK, INC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: BIOLAB COMPANY STORE, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: AQUA CLEAR INDUSTRIES, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: BIOLAB, INC., CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: CNK CHEMICAL REALTY CORPORATION, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110
Owner name: BIOLAB TEXTILES ADDITIVES, LLC, CONNECTICUT
Free format text: INTELLECTUAL PROPERTY SECURITY RELEASE AGREEMENT;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:026039/0142
Effective date: 20101110