Pentaerythritol derivative

The following formula characterizes structure of pentaerythritol plasticizers  

Main acids used in commercial products benzoic, butyric, mixture of C5, C7, Cg aUcanoic acids, fatty acids  

Main fields of application cable wire, thin-wall articles, plastisols  

Outstanding property low temperature flexibihty, oxidative stability, reduced smoke density  

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FIG. 4. Structures of trivalent tumor markers based on pentaerythritol derived with the Tn and the TF antigens.71... 

T. K. Lindhorst, M. Dubber, U. Krallmann-Wenzel, and S. Ehlers, Cluster mannosides as inhibitors of type 1 fimbriae-mediated adhesion of Escherichia coli Pentaerythritol derivatives as scaffolds, Eur. J. Org. Chem. (2000) 2027-2034. 

More generally applicable gamma-ray stabilisers have been claimed in the form of phosphorus-containing pentaerythritol derivatives, either alone [226] or in conjunction with a benzyl compound of the structure Ar-CHR-O-CHR-Ar [227]. 

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

The nameplate capacities for acetaldehyde production for the United States in 1989 are shown in Table 5 (120). Synthetic pyridine derivatives, peracetic acid, acetate esters by the Tischenko route, and pentaerythritol account for 40% of acetaldehyde demand. This sector may show strong growth in some products but all of these materials maybe prepared from alternative processes. 

Aminoalkoxy pentaerythritols are obtained by reduction of the cyanoethoxy species obtained from the reaction between acrylonitrile, pentaerythritol, and lithium hydroxide in aqueous solution. Hydrogen in toluene over a mthenium catalyst in the presence of ammonia is used (34). The corresponding aminophenoxyalkyl derivatives of pentaerythritol and trimethyl olpropane can also be prepared (35). 

Formaldehyde condenses with itself in an aldol-type reaction to yield lower hydroxy aldehydes, hydroxy ketones, and other hydroxy compounds the reaction is autocatalytic and is favored by alkaline conditions. Condensation with various compounds gives methylol (—CH2OH) and methylene (=CH2) derivatives. The former are usually produced under alkaline or neutral conditions, the latter under acidic conditions or in the vapor phase. In the presence of alkahes, aldehydes and ketones containing a-hydrogen atoms undergo aldol reactions with formaldehyde to form mono- and polymethylol derivatives. Acetaldehyde and 4 moles of formaldehyde give pentaerythritol (PE) ... 

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. 

Lubrication oil additives represent another important market segment for maleic anhydride derivatives. The molecular stmctures of importance are adducts of polyalkenyl succinic anhydrides (see Lubrication and lubricants). These materials act as dispersants and corrosion inhibitors (see Dispersants Corrosion and corrosion control). One particularly important polyalkenyl succinic anhydride molecule in this market is polyisobutylene succinic anhydride (PIBSA) where the polyisobutylene group has a molecular weight of 900 to 1500. Other polyalkenes are also used. Polyalkenyl succinic anhydride is further derivatized with various amines to produce both dispersants and corrosion inhibitors. Another type of dispersant is a polyester produced from a polyalkenyl succinic anhydride and pentaerythritol [115-77-5]. 

The principal valeraldehyde derivatives, -amyl and 2-methylbutyl alcohols, are used predominandy to make ziac diamyldithiophosphate lube oil additives (see Amyl alcohols Lubrication and lubricants), which are employed primarily in automotive antiwear appHcations. Similady, the / -valerate and 2-methylbutyrate esters of pentaerythritol and trimethylolpropane are used ia aeromotive synlube formulations and as refrigerant lubricants. 

Cy—oxo-derived acids are the principal derivatives of the C —oxo aldehydes, and ia analogy to oxo aldehyde market appHcations, are used chiedy to make neopolyol esters, ie, those based on neopentyl glycol, trimethylolpropane, or pentaerythritol. These synlubes are employed almost entirely ia aeromotive appHcations. Heptanoic acid is also employed to make tetraethylene glycol diheptanoate, a plasticizer used with poly(vinyl butyral). 

The newer HFC refrigerants are not soluble in or miscible with mineral oils or alkylbenzenes. The leading candidates for use with HFC refrigerants are polyol ester lubricants. These lubricants are derived from a reaction between an alcohol and a normal or branched carboxyflc acid. The most common alcohols used are pentaerythritol, trimethylolpropane, neopentjlglycol, and glycerol. The acids are usually selected to give the correct viscosity and fluidity at low temperatures. 

The most important derivatives of the carboxyl group are formed by esterification with monohydric or polyhydric alcohols. Typical alcohols used iaclude methyl alcohol, ethylene glycol, glycerol, and pentaerythritol. These rosia esters have a wide range of softening poiats and compatibiUties. 

Pentaerythritol with its four primary hydroxyl groups is used for the preparation of tetraesters and presents Httie difficulty except for its high melting point of 263°C, when pure. Pentaerythritol tetraesters are used in aircraft lubes, synthetic drying oils, and alkyds. Esters derived from trimethylo1 alkanes and dipentaerythritol are also used in alkyd resins (qv). Esterification may take place in situ during preparation of the alkyd. 

Pentaerythritol. Pentaerythritol tetranitrate, the tetranitrate derivative of 2,2-bis(hydroxymeth5l)-l-3-propanediol [115-77-5] is... 

The chloromethyl derivatives may be prepared from pentaerythritol via the trichloride or trichloride monoacetate (Figure 19.13). 

Rosins and rosin derivatives. The resins more commonly used in rubber base adhesives are rosin esters, particularly glycerol and pentaerythritol esters, as well as rosins modified by disproportionation and hydrogenation. The glycerol ester of hydrogenated rosin has been reported to be an excellent tackifier for polychloroprene adhesives (see pp. 344-357 in [17]). 

Coxon and Stoddart have directed their attention to the formation of penta-erythritol-derived cryptands. With these molecules, the strategy was to block one pair of hydroxyl groups as an acetal and form a crown from the remaining diol. In the first of the two reports cited above, this was accomplished by treating the 0-benzylidine derivative of pentaerythritol with base and diethylene glycol ditosylate. The crown was then treated with a mixture of UAIH4 and BF3 which gives partial reduction of the acetal as shown in (8.9), above. The monoprotected diol could now be treated in a fashion similar to that previously described and the benzyloxy cryptand (77) would result. The scheme is illustrated below as Eq. (8.10). 

PETN. Acronym for Pentaerythritol Tetra-nitrate. See under Pentaerythritol and its Derivatives in this Vol ... 

Polymerized Alcohols. Polyhydric alcohols (qv) such as pentaerythritol, sorbitol and glycerin can be used as the polyol component of polyethers (qv) which are used as expl and propint binders. Polyoxypropylene derivs of sorbitol have been employed extensively as components of polyurethane resins (qv), also employed as a propint binder... 

The analysis of pentaerythritols and brominated derivatives, which are fire retardants, may be performed by a number of techniques, some of which will be discussed here. Each procedure suffers from different drawbacks. The method chosen must answer the specific need of the analysis. We use the following abbreviations. 

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