Esters in plasticizers

The usual containers for shipping are glass for small quantities, and steel cans, dmms, or tank cars for bulk items. Over a period of time, moisture passes through the walls of some plastic containers. If this occurs, the more hydrolytically unstable borate esters may hydroly2e. Thus caution should be used when storing borate esters in plastic. In addition, shipping in metal cans or dmms is not acceptable where hydrolysis can lead to a corrosive product, such as a halogenated alcohol. 

Rastogi, S. C., Gas chromatographic analysis of phthalate esters in plastic toys, Chromatographia, Al, 724-726, 1998. 

White crystals m.p. 162-164 C. ll can be prepared by the fermentation of sugar with the mould Aspergillus lerreus or by healing citra-conic anhydride with water at ISO C. Electrolysis of the potassium salt in solution gives allene. Itaconic acid is used as a comonomer in plastics its esters are polymerized to lubricating oils and plasticizers. 

Reactions of the Methyl Groups. These reactions include oxidation, polycondensation, and ammoxidation. PX can be oxidized to both terephthahc acid and dimethyl terephthalate, which ate then condensed with ethylene glycol to form polyesters. Oxidation of OX yields phthaUc anhydride, which is used in the production of esters. These ate used as plasticizers for synthetic polymers. MX is oxidized to isophthaUc acid, which is also converted to esters and eventually used in plasticizers and resins (see Phthalic acids and otherbenzenepolycarboxylic acids). 

Plasticizers. About 2.5% of U.S. adipic acid consumed in 1988 was used in two basic types of adipic ester based plasticizers (195). Simple adipate esters prepared from Cg—alcohols are used especially as PVC plasticizers (qv). Eor special appHcations requiring low volatility or extraction resistance, polyester derivatives of diols or polyols are preferred. 

Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics hexanol and 2-ethylhexanol are used as part of the catalyst system in the polymerization of acrylates, ethylene, and propylene (55) the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization initiator for vinyl chloride various trialkyl phosphites find usage as heat and light stabHizers for plastics organotin derivatives are used as heat stabHizers for PVC octanol improves the compatibHity of calcium carbonate filler in various plastics 2-ethylhexanol is used to make expanded polystyrene beads (56) and acrylate esters serve as pressure sensitive adhesives. 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

The phosphonate esters, HP(=0(OR)2, of alkylated phenols are used extensively as lubricating-oil additives to control bearing corrosion and oxidation, and to impart antimst properties as stabilizers, as antioxidants (qv) and flame retardants in plastics, as specialty solvents, and as intermediates (see Corrosion AND corrosion control Heat stabilizers). 

Uses. Phthabc anhydride is used mainly in plasticizers, unsaturated polyesters, and alkyd resins (qv). PhthaUc plasticizers consume 54% of the phthahc anhydride in the United States (33). The plasticizers (qv) are used mainly with poly(vinyl chloride) to produce flexible sheet such as wallpaper and upholstery fabric from normally rigid polymers. The plasticizers are of two types diesters of the same monohydric alcohol such as dibutyl phthalate, or mixed esters of two monohydric alcohols. The largest-volume plasticizer is di(2-ethylhexyl) phthalate [117-81-7] which is known commercially as dioctyl phthalate (DOP) and is the base to which other plasticizers are compared. The important phthahc acid esters and thek physical properties are Hsted in Table 12. The demand for phthahc acid in plasticizers is naturally tied to the growth of the flexible poly(vinyl chloride) market which is large and has been growing steadily. 

Esters made from the reaction of acids (or anhydrides) with alcohols. 1-Alkanols produce linear chains, hence the L designation in plasticizer names. 

The role of specific interactions in the plasticization of PVC has been proposed from work on specific interactions of esters in solvents (eg, hydrogenated chlorocarbons) (13), work on blends of polyesters with PVC (14—19), and work on plasticized PVC itself (20—23). Modes of iateraction between the carbonyl functionaHty of the plasticizer ester or polyester were proposed, mostly on the basis of results from Fourier transform infrared spectroscopy (ftir). Shifts in the absorption frequency of the carbonyl group of the plasticizer ester to lower wave number, indicative of a reduction in polarity (ie, some iateraction between this functionaHty and the polymer) have been reported (20—22). Work performed with dibutyl phthalate (22) suggests an optimum concentration at which such iateractions are maximized. Spectral shifts are in the range 3—8 cm . Similar shifts have also been reported in blends of PVC with polyesters (14—20), again showing a concentration dependence of the shift to lower wave number of the ester carbonyl absorption frequency. 

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. 

Studies on the use of high molecular weight esters in nitrile mbber have led to further studies to compare DINP with DBP. These showed that at the 10 phr level the nitrile mbber was effectively plasticized with DINP (35). 

About one million tons of plasticizers aie used annually in Western Europe. Some 92% of this total is used to plasticize poly(vinyl chloride) (PVC) and about 95% of these PVC plasticizers are phthalate esters. In spite of the fact that there are several hundred plasticizers in commercial use in the world, only relatively few (ie, phthalates) are used in amounts that make them significant in toimage terms, and hence in their likely environmental input and impact. 

Acrylic ESTER POLYMERS Acrylonitrile POLYMERS Cellulose esters). Engineering plastics (qv) such as acetal resins (qv), polyamides (qv), polycarbonate (qv), polyesters (qv), and poly(phenylene sulfide), and advanced materials such as Hquid crystal polymers, polysulfone, and polyetheretherketone are used in high performance appHcations they are processed at higher temperatures than their commodity counterparts (see Polymers containing sulfur). 

CN is the oldest and most important inorganic ester of cellulose. It is a white, ododess, and tasteless substance. It has found uses in plastics, lacquers, and explosives. CN is manufactured by treating cellulose with nitric acid in the presence of sulfuric acid and water. The amount of water determines the DS attained (11,48,49). 

Plasticizers. Plasticizers are materials that soften and flexibilize inherently rigid, and even britde polymers. Organic esters are widely used as plasticizers in polymers (97,98). These esters include the benzoats, phthalates, terephthalates, and trimeUitates, and aUphatic dibasic acid esters. Eor example, triethylene glycol bis(2-ethylbutyrate) [95-08-9] is a plasticizer for poly(vinyl butyral) [63148-65-2] which is used in laminated safety glass (see Vinyl POLYMERS, poly(vinyl acetals)). Di(2-ethyUiexyl)phthalate [117-81-7] (DOP) is a preeminent plasticizer. Variation of acid and/or alcohol component(s) modifies the efficacy of the resultant ester as a plasticizer. In phthalate plasticizers, molecular sizes of the alcohol moiety can be varied from methyl to tridecyl to control permanence, compatibiUty, and efficiency branched (eg, 2-ethylhexyl, isodecyl) for rapid absorption and fusion linear (C6—Cll) for low temperature flexibiUty and low volatility and aromatic (benzyl) for solvating. Terephthalates are recognized for their migration resistance, and trimeUitates for their low volatility in plasticizer appHcations. 

Cresylic acid is mainly used as degreasing agent and as a disinfectant of a stabilized emulsion in a soap solution. Cresols are used as flotation agents and as wire enamel solvents. Tricresyl phosphates are produced from a mixture of cresols and phosphorous oxychloride. The esters are plasticizers for vinyl chloride polymers. They are also gasoline additives for reducing carbon deposits in the combustion chamber. 

SCRIMP process This Seeman Composites Resin Infusion Process (SCRIMP) is described as a gas-assist resin transfer molding process. As an example glass fiber fabrics/ thermoset vinyl ester polyester plastic and polyurethane foam panels (for insulation) are placed in a segmented tool. A vacuum is pulled with a bag so that a huge amount of plastic can be drawn into the mold (Marco process approach). Its curved roof is made separately and bonded to the box with mechanical and adhesive fastening. It is similar to various reinforced plastics molding processes. 

Similarly, organophosphate esters are used in a wide variety of applications including hydraulic fluids, plasticizers, and antiwear additives to hydraulic fluids and engine oils. All of these uses have the potential to contaminate the environment, and all of the organophosphate ester components present in hydraulic fluids also are present in plasticizers and antiwear additives. Therefore, detection of a particular organophosphate ester in the environment or in biological media cannot identify the source of the contamination (i.e., hydraulic fluids, plasticizers, antiwear additives). 

Si element ATR-FTIR spectroscopy was used to analyze this residue, and its spectrum, along with the closest library matches, are shown in Figure 41. The absorbance of this residue is low as a consequence of the thin layer present on the plate. This makes matching the sample spectrum with a reference spectrum somewhat difficult. The closest matches extracted from the library interrogated are to ester-based plasticizer materials, which is consistent with a phthalate-plasticized PVC. A more specific identification could have been made with further testing such as subjecting the residue to GC-MS analysis, but the information suggested by the ATR-FTIR analysis was, in this case sufficient. 

Used industrially for the manufacture of organophosphorus compounds (Insecticides, dyes, pharmaceuticals, defoliants) as well as esters for plasticizers, gasoline additives, and hydraulic fluids used in industry as a chlorinating agent, catalyst, dopant for semiconductor grade silicon, fire retarding agent, and solvent in cryoscopy. 

In terms of stability to organic solvents, P.Br.23 performs like other red pigments within its class. It is thus somewhat inferior to the yellow products. Regarding fastness to various ketones, esters, and alcohols, as well as to dioctyl phthalate and dibutyl phthalate, P.Br.23 equals step 3 1 and step 4, respectively, on the 5 step scale. P.Br.23 is broad in scope, but its main field of application is in plastics. 

Production, Import/Export, Use, Release, and Disposal. Because of the general confusion in the literature about the nomenclature for octylphthalate esters, historical information about the production and import/export of di- -octylphthalate is not readily available. These values generally must be estimated as a percentage of di(2-ethylhexyl)phthalate production or import/export. The compound is used principally as a plasticizer additive to plastics and PVC resins. It is also used as a dye carrier in plastics production and as a chemical intermediate (EPA 1993a HSDB 1995 Mannsville Chemical Products Corporation 1989 Sittig 1991). Limited information is available about releases of di-n-octylphthalate to environmental media. Even the TRI data, which comprise the most current information available, contain errors as a result of the nomenclature confusion (EPA 1993a Vista Chemical 1992). Data are available about the disposal and regulatory status of the compound (see Chapters 4 and 7). More information on the production and releases of di-ft-octylphthalate is needed to estimate potential exposure to the compound. 

Phthalate esters, particularly, di-2-ethylhexyl phthalate (DEHP), are widely used as plasticizers. The total annual U.S. production of phthalate esters was over h00,000 tons in 1970 (1). Many of the applications of phthalate esters such as in construction, home furnishings, the automobile industry, etc. make it likely that they reach the aquatic environment. Since the initial report of the presence of phthalate esters in natural waters and fish in the United States by Mayer and coworkers (2), there have been reports of these chemicals in fish in Canada (3, t) and in Japan (5). The presence of phthalate esters in the ocean waters off the United States and in Gulf of Mexico biota has also been noted (6. ... 

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