Stearate, Calcium

The above groups contain plasticizers which have several representatives of similar chemical structure. There still are plasticizers in common use or that were invented for specific purposes. These can be grouped as follows biphenyl derivatives,calcium stearate,carbon dioxide, difurans, fluorine-containing plasticizers, hydroxyben-zoic acid esters, isocyanate adducts, malonates, multi-ring aromatic 

Alkylation of biphenyl with cyclohexene gives dicyclohexylbiphenyl, which can be used as a secondary plasticizer for PVC. Synthesis of this plasticizer uses Friedel-Crafts reaction with aluminum chloride employed as a catalyst. The application data shows that weight loss and the retention of mechanical properties (tensile strength, elongation, and modulus) are greatly improved with this plasticizer. A mixture of di- and tri-alkyl (usually propyl) biphenyls is used as a plastieizer for polystyrene, butadiene rubber, epoxy resin, and polyurethane.  

Calcium stearate performs many functions in polymers. These include PVC costabilizer, lubricant of many polymers, release agent, etc. Polyamide-6, polyesters, polyethylene flow substantially better in the presence of calcium carbonate. Their mechanical properties 

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Lead(ll) azide Calcium stearate, copper, zinc, brass, carbon disulfide... 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

The test formulation contains 100 parts of PVC (Fikentscher K = 65), 1.2 parts of paraffin wax, 0.6 parts of calcium stearate, and 0.4 parts of methyitin-based stabilizers. 

The various lubricants formulated into PVC to improve the processing can also enhance the performance of the stabilizet. In pigmented apphcations, calcium soaps, eg, calcium stearate, ate commonly used as internal lubricants to promote PVC fusion and reduce melt viscosity. This additive is also a powerfiil costabilizer for the alkyl tin mercaptide stabilizers at use levels of 0.2 to 0.7 phr. Calcium stearate can significantly improve the eady color and increase the long-term stabiUty at low levels however, as the concentration increases, significant yellowing begins to occur. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

Rigid Applications. The use of the lead stabilizers is very limited in the United States but, they are stiU used in several rigid PVC appHcations in Europe and Asia. The highest use of lead stabilizers in rigid PVC is for pipe and conduit appHcations. Tribasic lead sulfate is the primary heat stabilizer with lead stearates included to provide lubrication. The lead products are typically fully formulated, usually including lubricants and pigments for pipe extmsion appHcations. These lead one-packs, when used at about 1.8—2.5 phr, provide all of the stabilizer and lubrication needed to process the polymer. A lead one-pack contains tribasic lead sulfate, dibasic lead stearate calcium stearate, polyethylene wax, paraffin wax, ester wax, and pigments. 

Two types of magnesia, caustic-calcined and periclase (a refractory material), are derived from dolomitic lime. Lime is required in refining food-grade salt, citric acid, propjiene and ethylene oxides, and ethylene glycol, precipitated calcium carbonate, and organic salts, such as calcium stearate, lactate, caseinate. 

Dry lubricants are usually added to the powder in order to decrease the friction effects. The more common lubricants include zinc stearate [557-05-17, lithium stearate [4485-12-5] calcium stearate [1592-23-0] stearic acid [57-11-4] paraffin, graphite, and molybdenum disulfide [1317-33-5]. Lubricants are generally added to the powder in a dry state in amounts of 0.25—1.0 wt % of the metal powder. Some lubricants are added by drying and screening a slurry of powder and lubricant. In some instances, lubricants are appHed in Hquid form to the die wall. 

Fig. 10. A model of PVC lubrication mechanism showing (a) PVC adhesion to metal without lubricant (b) surface activity of calcium stearate (c) nonmetal releasing character of paraffin only and (d) synergy between calcium stearate and paraffin (62).

Calcium carbonate Calcium hypochlorite Calcium stearate Expression belt 43 71... 

There has been a revival of interest in recent years in antimony mercaptides as alternatives to the organo-tin stabilisers. This stems from the low level of toxicity and the strong synergism with calcium stearate. However, compared to the... 

In Britain calcium stearate has been most commonly used with nontransparent products and stearic acid with transparent compounds. In the United States normal lead stearate, which melts during processing and lubricates like wax, is commonly employed. Dibasic lead stearate, which does not melt, lubricates like graphite and improves flow properties, is also used. 

Stearic acid and metal stearates such as calcium stearate are generally used as lubricants at a rate of about 1-3% on the total compound. Waxes such as camauba and ceresin or oils such as castor oil may also be used for this purpose. 

Lubricants. Lubricants such as wax or calcium stearate reduce the viscosity of the molten plastic and improve forming characteristics. 

The solubility of calcium carbonate is such that in a saturated solution the product of ion concentrations [Ca+2][C0 2] is 5 X I0 B. Though this may seem quite small, it is large enough to be important to man, especially if he lives in a region of the earth where there are extensive limestone deposits. Calcium carbonate can be dissolved in water, especially if it contains much dissolved C02. This is objectionable because soap added to water which contains even traces of Ca+2 forms a precipitate of calcium stearate. This is the ring that is so difficult to remove from the bathtub. 

Fig. 4. Dependence on filler concentration (

Many plastics because they are organic are flammable incorporate flame-retardants. Additives that contain chlorine, bromine, phosphorous, metallic salts, and so forth reduce the likelihood that combustion will occur or spread. Lubricants like wax or calcium stearate reduce the viscosity of molten plastic... 

Soaps are made by heating sodium hydroxide with a fat such as coconut oil, olive oil, or beef fat, which contain esters formed between glycerol and fatty acids (see Section 19.7). The sodium hydroxide attacks the esters and forms the soluble soap. In the case of beef fat, stearic acid forms the soap sodium stearate, seen in (3). Soaps, however, form a scum in hard water. The scum is an impure precipitate of calcium stearate. 

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