Acrylates butyl

Acrylates are still produced by a modified Reppe process that involves the reaction of acetylene, the appropriate alcohol (in the case of butyl acrylate, butyl alcohol is used), and carbon monoxide in the presence of an acid. The process is continuous, and a small amount of acrylates is made this way. 

The most economical method of acrylate production is that of the direct oxidation of propylene to acrylic acid, followed by esterification. 

Esters of acrylic acid (acrylates) are used for manufacture of coatings, textiles, fibers, polishes, paper, and leather. 

This alcohol can be reacted with methanol in the presence of a catalyst to produce methyl-r-butyl ether. Although it is currently cheaper to make Ao-butyl alcohol from Ao-butcne (Ao-butylene), it can be synthesized from syngas with alkali-promoted zinc oxide catalysts at temperatures above 400°C (750°F). 

Synonyms Acrylic acid butyl ester 2-propenoic acid butyl ester 

Physical Form. Colorless liquid with acrid odor commercial form contains hydroquinone (lOOOppm) or hydroquinone methyl ether (15 or 2 00 ppm) to prevent polymerization 

Manufacture of polymers and resins for textiles, paints, and leather finishes 

Toxicology. Butyl acrylate is an irritant of the eyes and skin. 

In one report, a woman with dermatitis from the plastic nose pads of her spectacle frames was found on patch testing to react to 1% butyl acrylate but not to ethyl or methyl acrylate. The sensitization was attributed to butyl acrylate, which might have been present in the plastic nose pads. 

Data were last reviewed in lARC (1986) and the compound was classified in lARC Monographs Supplement 7 (1987). 

141-32-2 Chem. Abstr. Name 2-Propenoic acid, butyl ester lUPAC Systematic Name Acrylic acid, n-butyl ester Synonym Butyl 2-propenoate 

2 Structural and molecular formulae and relative molecular mass 

From American Conference of Governmental Industrial Hygienists (1991) unless 

Production in the United States in 1993 was reported to be 340 035 tonnes (United 

In a 2-1. two-necked round-bottomed flask having a capillary ebullator tube in one neck (Note 1) arc placed 371 g. (5 moles) 

Sulfuric acid is also a very satisfactory catalyst aluminum alkoxides also are useful, especially when the alcohols would be adversely affected by strong acids. Sodium alkoxides produce undesirable side reactions and give lower yields. When alkaline catalysts are employed, an alkaline polymerization inhibitor, such as j j-phenylenediamine or phenyl-d-naphthylamine, should be used instead of hydroquinone. 

The methanol-methyl acrylate azeotrope contains about 45% methyl acrylate, which can be recovered by washing out the methanol with a large volume of water or brine the acrylate is purified by, drying and distilling. An inhibitor, such as hydro-quinone, should always be added to any acrylic ester before attempting to distil it, and, unless it is stored in a refrigerator, the distilled ester should not be kept more than a few hours without the addition of a small amount (0.1-1.0%) of an inhibitor. 

Yields of the primary alkyl acrylates vary somewhat, owing to occasional losses through formation of polymer, but are usually in the range of 85-99%. Some secondary alcohols react very slowly, others readily. The method has been applied to more than fifty alcohols, some of which (with percentage yields) are listed below ethyl, 99% isopropyl, 37% -amyl, 87% isoamyl, 95% -hexyl, 99% 4-methyl-2-pentyl, 95% 2-ethylhexyl, 95% capryl, 80% lauryl, 92% myristyl, 90% allyl, 70% fur-furyl, 86% citronellyl, 91% cyclohexyl, 93% benzyl, 81% (3-ethoxyethyl, 99% /S-(/3-phenoxyethoxy) ethyl (from diethylene glycol monophenyl ether), 88%. 

DI-( -CHLOROPHENyL)-ACETIC ACID (Acetic acid, di-(/i-chlorophenyl)) 

Rohm and Haas Chemical has about one-quarter of the world productive capacity with its plant at Deer Park, Texas. Dow Chemical and BASF between them share about one-third of the productive capacity. There is a total of about 26 production plants throughout the world located in the United States, France, Brazil, Germany, Malaysia, China, Japan, Russia, Indonesia, Czech Repubic, and Singapore. 

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Temperature, °C Acryhc acid Methyl acrylate Ethyl acrylate Butyl acrylate 2-EthyIhexyl acrylate... 

Esterifica.tlon. The process flow sheet (Fig. 4) outlines the process and equipment of the esterification step in the manufacture of the lower acryflc esters (methyl, ethyl, or butyl). For typical art, see References 69—74. The part of the flow sheet containing the dotted lines is appropriate only for butyl acrylate, since the lower alcohols, methanol and ethanol, are removed in the wash column. Since the butanol is not removed by a water or dilute caustic wash, it is removed in the a2eotrope column as the butyl acrylate a2eotrope this material is recycled to the reactor. 

Process conditions for methyl acrylate are similar to those employed for ethyl acrylate. However, in the preparation of butyl acrylate the excess butanol is removed as the butanol—butyl acrylate a2eotrope in the a2eotrope column. 

Mechanical and Thermal Properties. The first member of the acrylate series, poly(methyl acrylate), has fltde or no tack at room temperature it is a tough, mbbery, and moderately hard polymer. Poly(ethyl acrylate) is more mbberflke, considerably softer, and more extensible. Poly(butyl acrylate) is softer stiU, and much tackier. This information is quantitatively summarized in Table 2 (41). In the alkyl acrylate series, the softness increases through n-octy acrylate. As the chain length is increased beyond n-octy side-chain crystallization occurs and the materials become brittle (42) poly( -hexadecyl acrylate) is hard and waxlike at room temperature but is soft and tacky above its softening point. 

Under conditions of extreme acidity or alkalinity, acryhc ester polymers can be made to hydroly2e to poly(acryhc acid) or an acid salt and the corresponding alcohol. However, acryhc polymers and copolymers have a greater resistance to both acidic and alkaline hydrolysis than competitive poly(vinyl acetate) and vinyl acetate copolymers. Even poly(methyl acrylate), the most readily hydroly2ed polymer of the series, is more resistant to alkah than poly(vinyl acetate) (57). Butyl acrylate copolymers are more hydrolytically stable than ethyl acrylate copolymers (58). 

Methyl acrylate Ethyl acrylate Butyl acrylate... 

Emulsion Polymerization. Emulsion polymerization is the most important industrial method for the preparation of acryhc polymers. The principal markets for aqueous dispersion polymers made by emulsion polymerization of acryhc esters are the paint, paper, adhesives, textile, floor pohsh, and leather industries, where they are used principally as coatings or binders. Copolymers of either ethyl acrylate or butyl acrylate with methyl methacrylate are most common. 

Numerous recipes have been pubUshed, primarily ia the patent Hterature, that describe the preparation of acrylate and methacrylate homopolymer and copolymer dispersions (107,108). A typical process for the preparation of a 50% methyl methacrylate, 49% butyl acrylate, and 1% methacrylic acid terpolymer as an approximately 45% dispersion ia water begias with the foUowiag charges ... 

In 1989 the U.S. prices for ethyl and butyl acrylate were in the range of 1.20 to 1.50/kg. Lower volume acrylates generally ranged in price from 3.00 to 5.00/kg. Prices for acryUc polymers are generally one and one-half to three times the monomer costs. 

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. 

AH-acryHc (100%) latex emulsions are commonly recognized as the most durable paints for exterior use. Exterior grades are usuaHy copolymers of methyl methacrylate with butyl acrylate or 2-ethyIhexyl acrylate (see Acrylic ester polymers). Interior grades are based on methyl methacrylate copolymerized with butyl acrylate or ethyl acrylate. AcryHc latex emulsions are not commonly used in interior flat paints because these paints typicaHy do not require the kind of performance characteristics that acryHcs offer. However, for interior semigloss or gloss paints, aH-acryHc polymers and acryHc copolymers are used almost exclusively due to their exceUent gloss potential, adhesion characteristics, as weU as block and print resistance. 

Vinyl acetate is another monomer used in latex manufacture for architectural coatings. When copolymerized with butyl acrylate, it provides a good balance of cost and performance. The interior flat latex paint market in North America is almost completely dominated by vinyl acetate—acryHc copolymers. Vinyl acetate copolymers are typicaHy more hydrophilic than aH-acryHc polymers and do not have the same ultraviolet light resistance as acryHcs as a result. 

Studies of the particle—epoxy interface and particle composition have been helphil in understanding the mbber-particle formation in epoxy resins (306). Based on extensive dynamic mechanical studies of epoxy resin cure, a mechanism was proposed for the development of a heterophase morphology in mbber-modifted epoxy resins (307). Other functionalized mbbers, such as amine-terminated butadiene—acrylonitrile copolymers (308) and -butyl acrylate—acryhc acid copolymers (309), have been used for toughening epoxy resins. 

Acrylic Elastomers. AcryHc elastomers possess good oU and heat resistance. They ate made by polymeti2ing monomeric acid esters of ethyl or butyl acrylate and methoxyethyl acrylate or ethoxyethyl acrylate. They can be polymeti2ed in emulsion, suspension, or solution systems (9) (see... 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

N. J. Earhart, The Grafting Reactions ofPoly(vinyl alcohol) During the Emulsion Copolymerisyation of Poly(vinyl acetate—co-butyl acrylate), Ph.D. dissertation. 

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