Poly lubrication

Alkylated aromatic lubricants, phosphate esters, polyglycols, chlorotrifluoroethylene, siUcones, and siUcates are among other synthetics that came into production during much that same period (28,29). Polyphenyl ethers and perfluoroalkyl polyethers have followed as fluids with distinctive high temperature stabiUty. Although a range of these synthetic fluids find appHcations which employ their unique individual characteristics, total production of synthetics represent only on the order of 2% of the lubricant market. Poly(a-olefin)s, esters, polyglycols, and polybutenes represent the types of primary commercial interest. 

Poly(alkylene glycol)s have a number of characteristics that make them desirable as lubricants. Compared to petroleum lubricants, they have lower pour points, a higher viscosity index, and a wider range of solubilities including water, compatibility with elastomers, less tendency to form tar and sludge, and lower vapor pressure (35). 

Poly(alkylene glycol)s are also used as lubricity additives ia water-based synthetic cutting and grinding fluids (36), and ia aqueous metalworking fluids. Under the high frictional heating at the tool or die contact with the workpiece, the polyalkylene glycol comes out of solution ia fine droplets which coat the hot metal surfaces. 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

The even-numbered carbon alpha olefins (a-olefins) from through C q are especially useful. For example, the C, C, and Cg olefins impart tear resistance and other desirable properties to linear low and high density polyethylene the C, Cg, and C q compounds offer special properties to plasticizers used in flexible poly(vinyl chloride). Linear C q olefins and others provide premium value synthetic lubricants linear 145 olefins are used in... 

Ghdants are needed to faciUtate the flow of granulation from the hopper. Lubricants ensure the release of the compressed mass from the punch surfaces and the release/ejection of the tablet from the die. Combinations of siUcas, com starch, talc (qv), magnesium stearate, and high molecular weight poly(ethylene glycols) are used. Most lubricants are hydrophobic and may slow down disintegration and dmg dissolution. 

Poly(ethylene terephthalate). PET is a crystalline material and hence difficult to plasticize. Additionally, since PET is used as a high strength film and textile fiber, plasticization is not usually required although esters showing plasticizing properties with PVC may be used in small amounts as processing aids and external lubricants. Plasticizers have also been used to aid the injection mol ding of PET, but only at low concentrations. 

Poly(vinyl chloride). PVC is one of the most important and versatile commodity polymers (Table 4). It is inherently flame retardant and chemically resistant and has found numerous and varied appHcations, principally because of its low price and capacity for being modified. Without modification, processibiUty, heat stabiUty, impact strength, and appearance all are poor. Thermal stabilizers, lubricants, plasticizers, impact modifiers, and other additives transform PVC into a very versatile polymer (257,258). 

Eatty acid ethoxylates are used extensively in the textile industry as emulsifiers for processing oils, antistatic agents (qv), softeners, and fiber lubricants, and as detergents in scouring operations. They also find appHcation as emulsifiers in cosmetic preparations and pesticide formulations. Eatty acid ethoxylates are manufactured either by alkaH-catalyzed reaction of fatty acids with ethylene oxide or by acid-catalyzed esterification of fatty acids with preformed poly(ethylene glycol). Deodorization steps are commonly incorporated into the manufacturing process. 

The fabric is desized after the weaving operation and then passed through a heated water bath to remove all the size. The rate at which this operation can be accompHshed depends to a great degree on solubiUty rate of the poly(vinyl alcohol). Difficulties encountered in completely removing the lubricating wax, usually tallow wax, has led to the development of several wax-free size compositions (303—311). The main component contained in these blends is PVA in combination with a small amount of a synthetic water-soluble lubricant. 

Graphite fluoride continues to be of interest as a high temperature lubricant (6). Careful temperature control at 627 3° C results in the synthesis of poly(carbon monofluoride) [25136-85-0] (6). The compound remains stable in air to ca 600°C and is a superior lubricant under extreme conditions of high temperatures, heavy loads, and oxidising conditions (see Lubrication and lubricants). It can be used as an anode for high energy batteries (qv). 

Oxidized castor oils are excellent nonmigrating, nonvolatile plasticizers (qv) for ceUulosic resins, poly(vinyl butyral), polyamides, shellac, and natural and synthetic mbber (see Rubber, natural). The high viscosity products are also used as tackifiers in gasket compounds and adhesives (qv) because of good oil and solvent resistance. They also serve as excellent pigment grinding media and as a base for inks (qv), lubricating oils, and hydrauHc oils (62). 

Diesters. Many of the diester derivatives are commercially important. The diesters are important plasticizers, polymer intermediates, and synthetic lubricants. The diesters of azelaic and sebacic acids are useflil as monomeric plasticizing agents these perform weU at low temperatures and are less water-soluble and less volatile than are diesters of adipic acid. Azelate diesters, eg, di- -hexyl, di(2-ethylhexyl), and dibutyl, are useflil plasticizing agents for poly(vinyl chloride), synthetic mbbers, nitroceUulose, and other derivatized ceUuloses (104). The di-hexyl azelates and dibutyl sebacate are sanctioned by the U.S. Food and Dmg Administration for use in poly(vinyl chloride) films and in other plastics with direct contact to food. The di(2-ethylhexyl) and dibenzyl sebacates are also valuable plasticizers. Monomeric plasticizers have also been prepared from other diacids, notably dodecanedioic, brassyflc, and 8-eth5lhexadecanedioic (88), but these have not enjoyed the commercialization of the sebacic and azelaic diesters. 

Miscellaneous Commercial Applications. Dimer acids are components of "downweU" corrosion inhibitors for oil-drilling equipment (see Petroleum Corrosion and corrosion inhibitors). This may account for 10% of current dimer acid use (71). The acids, alkyl esters, and polyoxyalkylene dimer esters are used commercially as components of metal-working lubricants (see Lubrication). Dimer esters have achieved some use in specialty lubricant appHcations such as gear oils and compressor lubricants. The dimer esters, compared to dibasic acid esters, polyol esters and poly(a-olefin)s, are higher in cost and of higher viscosity. The higher viscosity, however, is an advantage in some specialties, and the dimer esters are very stable thermally and can be made quite oxidatively stable by choice of proper additives. 

More than half the metal stearates produced in the United States are appHed as lubricants and heat stabili2ers (qv) in plastics, particularly in the processing of poly(vinyl chloride) (PVC) resins. 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

Fouling Industrial streams may contain condensable or reactive components which may coat, solvate, fill the free volume, or react with the membrane. Gases compressed by an oil-lubricated compressor may contain oil, or may be at the water dew point. Materials that will coat or harm the membrane must be removed before the gas is treated. Most membranes require removal of compressor oil. The extremely permeable poly(trimethylsilylpropyne) may not become a practical membrane because it loses its permeability rapidly. Part of the problem is pore collapse, but it seems extremely sensitive to contamination even by diffusion pump oil and gaskets [Robeson, op. cit., (1994)]. 

A number of higher n-alkyl methacrylate polymers have found commercial usage. The poly-(n-butyl-), poly-(n-octyl-) and poly-(n-nonyl methacrylate)s have found use as leathering finishes whilst polyflauryl methacrylate) has become useful as a pour-point depressant and improver of viscosity temperature characteristics of lubricating oils. 

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