2 ethyl acrylate

Synonyms Ethyl 2-propenoate 2-propenoic acid ethyl ester acrylic acid ethyl ester 

A monomer widely used in the production of polymers and copolymers for manufacturing textiles, latex paints, paper coatings, dirt release agents, and specialty plastics 

The vapor is moderately irritating at 4 ppm, and it is believed that workers would not tolerate 25 ppm for any length of time. However, in another report, prolonged exposure to 50-75 ppm supposedly produced drowsiness, headache, and nausea. Skin sensitization has occurred from industrial exposure a 4% concentration in petrolatum produced sensitization reactions in 10 of 24 volunteers.  

In rats, 2 000 ppm for 4 hours was fatal, with death attributed to severe pulmonary irritation 1000 ppm for 4 hours was not fatal but caused irritation of the skin. Repeated exposure to 500ppm was fatal to rats, and 275 ppm was lethal to rabbits and guinea pigs. Irritation of the eyes, nose, and mouth as well as lethargy, dyspnea, and convulsive movements preceded death. At autopsy, there was pulmonary edema and degenerative changes in liver, kidneys, and heart muscle. The epidermis and dermis are the primary target tissues when the liquid is applied to the skin. 

Gavage administration of a single dose causes profound gastric toxicity that includes concentration- and time-dependent mucosal 

Ethane is dehydrogenated to produce ethylene, which is reacted with benzene to make ethylbenzene for styrene production, generating an important feedstock to manufacture SBR rubber and SBS and SIS block polymers used as TPEs by the rubber industry. 

Ethane is dehydrogenated to produce ethylene, which is used to produce EPDM, CM, CSM, EAM, and FKM elastomers and SEBS, SEPS, and SEPS block-polymer thermoplastic elastomers. Also, EPDM is used to make thermoplastic vulcanizates by dynamic vulcanization with polypropylene. 

Ethane is also used as a fuel source and a very important general petrochemical 

Merck Schuchardt OHG (Germany) Chemos GmbH (Germany) 

Ethyl acrylate is one of the monomers used to produce ACM rubber. Nonrubber Uses 

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

140-88-5 Chem. Abstr. Name 2-Propenoic acid, ethyl ester lUPAC Systematic Name Acrylic acid, ethyl ester Synonym Ethyl propenoate 

2 Structural and molecular formulae and relative molecular mass 

Production of ethyl acrylate in the United States in 1993 was reported to be 160 345 

Ethyl acrylate is used as a monomer in acrylic resins (American Conference of Governmental Industrial Hygienists, 1991). 

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CgH,oN20. Colourless crystalline solid, m.p. 121 °C. Made by reacting phenylhydrazine with ethyl acrylate to obtain the hydrazide which cyclizes to the product. Its major commercial importance is as a photographic developing agent, being used particularly in conjunction with hydroquinone. 

Indoles can also be alkylated by conjugate addition under alkaline conditions. Under acidic conditions, alkylation normally occurs at C3 (see Section 11.1). Table 9.1 includes examples of alkylation by ethyl acrylate, acrylonitrile, acrylamide and 4-vinylpyridine. 

Reaction of 2-aminothiazole with ethyl acrylate yields 5.6-dihydro-7H-thiazolo[3,2a]pyrimidin-7-one (116) (Scheme 78) (169). 

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

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. 

Acetylene-Based Routes. Walter Reppe, the father of modem acetylene chemistry, discovered the reaction of nickel carbonyl with acetylene and water or alcohols to give acryUc acid or esters (75,76). This discovery led to several processes which have been in commercial use. The original Reppe reaction requires a stoichiometric ratio of nickel carbonyl to acetylene. The Rohm and Haas modified or semicatalytic process provides 60—80% of the carbon monoxide from a separate carbon monoxide feed and the remainder from nickel carbonyl (77—78). The reactions for the synthesis of ethyl acrylate are... 

The stoichiometric and the catalytic reactions occur simultaneously, but the catalytic reaction predominates. The process is started with stoichiometric amounts, but afterward, carbon monoxide, acetylene, and excess alcohol give most of the acrylate ester by the catalytic reaction. The nickel chloride is recovered and recycled to the nickel carbonyl synthesis step. The main by-product is ethyl propionate, which is difficult to separate from ethyl acrylate. However, by proper control of the feeds and reaction conditions, it is possible to keep the ethyl propionate content below 1%. Even so, this is significantly higher than the propionate content of the esters from the propylene oxidation route. 

The relatively low flash points of some acrylates create a fire hazard. Also, the ease of polymerization must be home in mind in ah. operations. The lower and upper explosive limits for methyl acrylate are 2.8 and 25 vol %, respectively. Corresponding limits for ethyl acrylate are 1.8 vol % and saturation, respectively. All possible sources of ignition of monomers must be eliininated. 

In 1983 the National Toxicology Program (NTP) reported that ethyl acrylate produced tumors in the rodent forestomach after gavage (forced... 

Historically, the development of the acrylates proceeded slowly they first received serious attention from Otto Rohm. AcryUc acid (propenoic acid) was first prepared by the air oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(methyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acryUc polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reaUty. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Rohm s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

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... 

Table 10. Chain-Transfer Constants to Common Solvents for Poly(ethyl acrylate) ...

A typical process for the preparation of a 94.8% ethyl acrylate—5.2% acryUc acid copolymer as an approximately 39% solution in ethyl acetate is given... 

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. 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

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