CALCIUM SULFONATE

Detergents are metal salts of organic acids used primarily in crankcase lubricants. Alkylbenzenesulfonic acids, alkylphenols, sulfur- and methjiene-coupled alkyl phenols, carboxyUc acids, and alkylphosphonic acids are commonly used as their calcium, sodium, and magnesium salts. Calcium sulfonates, overbased with excess calcium hydroxide or calcium carbonate to neutralize acidic combustion and oxidation products, constitute 65% of the total detergent market. These are followed by calcium phenates at 31% (22). 

Chemical Name 2,5-dihydroxybenzenesulfonic acid calcium salt Common Name Hydroquinone calcium sulfonate Structural Formula oh f" ... 

At the end of the addition, an almost colorless ether layer swims on the surface of the strongly colored water layer. After removal of the ether layer, the water layer is concentrated to dryness under vacuum and a stream of an inert gas. An earthy precipitate is formed, which after recrystallization yields 100 grams of hydroquinone calcium sulfonate, which decomposes without melting above 250°C. 

Physical Form, brown to black oily liquid new mineral-based crankcase oil contains petrochemicals (straight-chain hydrocarbons, aromatic hydrocarbons, and polyaromatic hydrocarbons or PAH) plus stabilizers and detergents including zinc dithiophosphate, zinc diaryl or dialkyl dithiophosphates (ZTDP), calcium alkyl phenates, magnesium, sodium, and calcium sulfonates, tricresyl phosphates, molybdenum disulfide, heavy metal soaps, cadmium, and zinc. ... 

Calcium Overbased calcium sulfonate and calcium phenate-detergent/acid neutralizing additive... 

Engine lubricant formulators are aware of the problems associated with fuel sulfur and develop products to help combat its corrosive effect. Lubricants containing overbased calcium sulfonates and phenates are utilized to chemically neutralize the acids which form as a result of burning fuel sulfur. These oils can be effective at preventing the corrosive effects of fuel sulfur. However, the oils must be frequently changed to ensure that the acid-neutralizing effect is maintained. 

The detergent effect of barium and calcium sulfonates in heavy-duty lubricating oils, particularly those used in Diesel equipment, is evidenced by the striking decrease in engine deposits and ring fouling resulting from their use (8). 

Appropriately functionalized resins can sequester excess nucleophiles from solution-phase reactions. Thus the calcium sulfonate resin 4 captures tetra-n-butylammonium fluoride (TBAF) from a variety of desilylation reactions.22,24 Polymer-bound tetra-n-butylammonium sulfonate and insoluble calcium fluoride are formed. The applicability of this strategy was illustrated for deprotection of (3-trimethylsilylethyl esters as well as silyl ethers. 

TBAF-quenching calcium sulfonate resin 4 and acidic-quench resin 51 in step 4 and... 

Other types of inverse micelles, such as those of egg yolk phosphatidylcholine (87) and a calcium alkylarylsulfonate (88) have also been investigated. As recently discussed (88), the properties of inverse micelles formed by different surfactant molecules should be expected to be quite diverse. As an example, the interaction of a solubilizate (TbCl3) with surfactant headgroups of the calcium sulfonate surfactant mentioned above was found by FT-IR and energy transfer methods to be dramatically slower (10-150 hr) than that found with AOT (milliseconds). 

Table 2.2. Typical parameter values for calcium sulfonates, alkylphenyl sulfides and alkylsalicylates detergents with additional total base number (TBN, mgKOH/g oil) from calcium carbonate. Formation of hard-core reverse micelles (RMs) of calcium carbonate-sulfonate or alkylphenate and soft-core revere micelles (RMs) of calcium alkylsalicylate in oil formulations...

The XANES spectra of the tribofilms were recorded in the bulk FY mode, and in the surface TEY mode from the ZDDP and calcium phenate. The (S) L-edge and (P) L-edge XANES spectra indicate that sulfur in sulfide form was only present on the topmost part of the film the phosphorus signaled that the topmost surface contained relatively long polyphosphates, and the bulk chemistry of the film contained mostly shorter-chain polyphosphates. Using a range of concentrations of two detergents, it was concluded that calcium phenate influences the film formation much more than calcium sulfonate, and thus calcium phenate solubilize excess ZDDP from film surfaces more effectively (Yin et al., 1997). 

Calcium sulfonate RMs (c < 2%) + ZDDP - polyphosphate tribofilm and unreacted ZDDP ... 

With the selection of proper water content and reaction temperature, a new type of hard-core RMs sulfonates which contained an ultrafine calcium borate as an alkaline component was prepared. Since both reactants, calcium hydroxide and boric acid, are oil insoluble, water is necessary as a reaction medium in the presence of neutral calcium sulfonates. When water content was less than 5% of the sulfonates used, the rate of the reaction was too low and unreacted materials were present in significant quantity as coarse particles. With the water content... 

X-ray absorption study of tribofilms generatedfrom a combination of ZDDP and borate-sulfonate RMs was used to determine the chemistry of tribochemical films at the surface and the bulk The calcium phosphate content in the tribofilm generated from either ZDDP + borate-sulfonate RMs or from ZDDP + calcium sulfonate soft-core RMs is similar (Varlot et al., 2001). Calcium sulfonate S(+5) undergoes disproportion reaction to form sulfate S(+6) and sulfite S(+4), and the presence of ZDDP affects the disproportion process. Close to the steel surface, the... 

ZDDP + calcium sulfonate ZDDP + calcium borate-sulfonate... 

Comparative friction tests under boundary conditions suggest three types of interactions between ZDDP and carbonate-sulfonate RMs in the oil phase (Kapsa et al., 1981) (a) chemical interactions between ZDDP and hard-core RMs of carbonate-sulfonate lead to an effective ZDDP concentration decrease (b) the detergent effect due to the presence of calcium sulfonate molecules prevents materials from agglomeration during running (c) the specific role of the hard-core reverse micelles. 

The ratio R = (Thickness worn before and during films formation) / (thickness worn after films formation) e.g., R value of the calcium sulfonate = 3.9 nm / 1.5... 

Table 4.4. The tribochemical effect of micellar additives (calcium sulfonate, calcium phenate) + ZDDP (1.2 wt%) on the polyphosphate chain length from XANES spectrum measured in the bulk FY technique and in surface TEY technique (Yin et al., 1997b)...

Calcium sulfonate or Calcium phenate (wt%) Tribofilm composition (%) unreacted ZDDP Chain length, number of (P). Surface (TEY) 5 nm Calcium sulfonate Chain length, number of (P) Bulk (FY) 50 nm Calcium phenate... 

Tribofilm composition Explain the polyphosphate chain length in the bulk and on the surface when ZDDP is in the presence of calcium sulfonate and calcium phenolate soft-core RMs (for solution see Table 4.4). 

TestB Acid neutralization test. The same three field test formulations, identical in every way except for the detergent, were treated with 5 TAN of oleic acid (a weak organic acid) and titrated for TAN by method D664. In addition, the same amount of acid was added to the base oil as a reference. As shown in Table 6.7, the magnesium sulfonate did not reduce the TAN at all over the base oil case. The greatest reduction in TAN was observed with calcium phenate, but calcium sulfonate also provided a meaningful reduction in TAN. This is the same ranking as the TAN increase observed in the field test. 

Hard-core reverse micelles are composed of detergent molecules, e.g., calcium sulfonate strongly bonded to calcium carbonate core detergent layer of 2.2 nm, hard-core diameter of 3.9 nm, total diameter of 8.2 nm. 

PVC plastisols or pastes should have a viscosity suitable for handling and storage, as well as the manufacturing process. This is necessary for thinning under the appropriate shear conditions. Paste PVC resins (or blends of resins) are designed to satisfy a particular rheology profile, but sometimes the addition of viscosity modifiers is necessary. Fumed silicas are typically used. Calcium sulfonate gels have also been promoted (458). 

Alkyd GridGard 2600 Carboline Alkyd/Calcium sulfonate... 

A great advantage of such systems as that based on calcium sulfonate resins is that it is a purely physical phenomenon, in the sense that no permanent change occurs in the resin from cycle to cycle. In principle, the resins do not require regeneration, and should be usable for many cycles of operation. 

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