Acrylate, ethyl methyl

The polymeric products can be made to vary widely in physical properties through controlled variation in the ratios of monomers employed in thek preparation, cross-linking, and control of molecular weight. They share common quaHties of high resistance to chemical and environmental attack, excellent clarity, and attractive strength properties (see Acrylic ester polymers). In addition to acryHc acid itself, methyl, ethyl, butyl, isobutyl, and 2-ethylhexyl acrylates are manufactured on a large scale and are available in better than 98—99% purity (4). They usually contain 10—200 ppm of hydroquinone monomethyl ether as polymerization inhibitor. 

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

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

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. 

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. 

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... 

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. 

An a priori method for choosing a surfactant was attempted by several researchers (50) using the hydroph i1 e—1 ip oph i1 e balance or HLB system (51). In the HLB system a surfactant soluble in oil has a value of 1 and a surfactant soluble in water has a value of 20. Optimum HLB values have been reported for latices made from styrene, vinyl acetate, methyl methacrylate, ethyl acrylate, acrylonitrile, and their copolymers and range from 11 to 18. The HLB system has been criticized as being imprecise (52). 

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. 

Intrinsic viscosity—molecular weight relationships have been obtained for copolymers in methyl ethyl ketone. The value for a 15 wt % ethyl acrylate (EA) copolymer is [77] = 2.88 x 10 . ... 

Butyl acrylate has been prepared by direet esterifieaLion/ by debromination of -butyl ,/3-dibromopropionate with zinc, by treatment of either butyl /3-chloropropionate or butyl /3-bromopropionate with diethylaniline, and by the pyrolysis of butyl (3-acetoxypropionated Direct esterification and alcoholysis of methyl or ethyl acrylate have been recommended for the preparation of the higher alkyl acrylates. ... 

By copolymerising with a small amount of second monomer which acts as an obstruction to the unzipping reaction, in the event of this being allowed to start. On the industrial scale methyl methacrylate is sometimes copolymerised with a small amount of ethyl acrylate, and formaldehyde copolymerised with ethylene oxide or 1,3-dioxolane for this very reason. 

Methyl, ethyl and allyl acrylate were first prepared in 1873 by Caspary and Tollens, and of these materials the last was observed to polymerise. In 1880 Kahlbaum reported the polymerisation of methyl acrylate and at approximately the same time Fittig found that methacrylic acid and some of its derivatives readily polymerised. 

A number of thermosetting acrylic resins for use as surface coatings have appeared during recent years. These are generally complex copolymers and terpolymers such as a styrene-ethyl acrylate-alkoxy methyl acrylamide... 

A number of other copolymers with vinylidene chloride as the major component have been marketed. Prominent in the patent literature are methyl methacrylate, methyl acrylate and ethyl acrylate. 

A number of higher poly(vinyl ether)s, in particular the ethyl and butyl polymers, have found use as adhesives. When antioxidants are incorporated, pressure-sensitive adhesive tapes from poly(vinyl ethyl ether) are said to have twice the shelf life of similar tapes from natural rubber. Copolymers of vinyl isobutyl ether with methyl acrylate and ethyl acrylate (Acronal series) and with vinyl chloride have been commercially marketed. The first two products have been used as adhesives and impregnating agents for textile, paper and leather whilst the latter (Vinoflex MP 400) has found use in surface coatings. 

Group of plastics based on resins generated from the polymerization of acrylic monomers (e.g., ethyl acrylate and methyl methacrylate). 

The addition of diazomethane to unsaturated esters (1), as ethyl acrylate, methyl crotonate and ethyl cinnamate, was investigated by Auwers who showed that the primary addition product is a A -pyrazoline (2) which rearranges spontaneously to the conjugated A -pyrazoline (3). 

The reaction of methyl or ethyl acrylate with the enamine of an alicyclic ketone results in simple alkylation when the temperature is allowed to rise uncontrolled in the reaction mixture (7,34,35). If the reaction mixture is kept below 30°C, however, a mixture of the simple alkylated and cyclobutane (from 1,2 cycloaddition) products are obtained (34). Upon distillation of this mixture only starting material and simple alkylated product is obtained because of the instability of the cyclobutane adduct. 

The addition of ethyl acrylate to 1,2-dimethyl- -piperideine 163), l-methyl-2-ethyl-zJ -piperideine 164), and 1,2-dimethyl- -pyrrolidine 216,217) occurs, yielding both possible enamine structures (138 and 139, n=I,2). 

An interesting addition of ethyl acrylate has been reported in the case of l-methyl-2-ethylidenepyrrolidine. An unsaturated amino ketone 144 is formed, which rearranges to 1,7-dimethyloctahydroindole (145) on reduction with formic acid, as established by dehydrogenation to 1,7-dimethyl-indole (Scheme 12) 217). 

Graft copolymerization of acrylonitrile with various vinyl comonomers such as methyl acrylate, ethyl acrylate, vinyl acetate, and styrene onto cellulose derivatives using ceric ion was studied [24]. The results showed that... 

Methyl ethyl ketone may also he produced hy the catalyzed dehydrogenation of sec-hutanol over zinc oxide or brass at about 500°C. The yield from this process is approximately 95%. MEK is used mainly as a solvent in vinyl and acrylic coatings, in nitrocellulose lacquers, and in adhesives. It is a selective solvent in dewaxing lubricating oils where it dissolves the oil and leaves out the wax. MEK is also used to synthesize various compounds such as methyl ethyl ketone peroxide, a polymerization catalyst used to form acrylic and polyester polymers and methyl pentynol by reacting with acetylene ... 

Irradiation of complex 6 in the presence of ethyl acrylate provides the [6 + 2] 7t-adduct 9 as the single enrfo-diastereomer,276 which may also be obtained by heating a mixture of methyl l//-azepine-l-carboxylate with the ester in the presence of a catalytic amount of tricarbonyl(>]6-naphthalene)chromium(O).277... 

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