Ethyl acrylate polymerization

The ethyl acrylate polymerization rate remains constant up to 38-40% conversion (Fig. 17), whereas according to data on equilibrium swelling of etbyl acrylate latex particles (Mamadaliev, 1978) the monomer phase disappears at 20% conversion. Hence, the polymerization rate remains constant after the disappearance of the monomer drops. Since the monomer drops... 

The logarithmic dependence of the ethyl acrylate polymerization rate on concentration of emulsifiers of various chemical structure is shown in Fig. 19 (Yeliseyeva et al, 1976). Polymerization was carried out in a dilatometer... 

On the basis of tbe data presented tbe kinetic equation f[Pg.283]

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. 

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. 

The earliest study describing vulcanised polymers of esters of acryUc acid was carried out in Germany by Rohm (2) before World War I. The first commercial acryUc elastomers were produced in the United States in the 1940s (3—5). They were homopolymers and copolymers of ethyl acrylate and other alkyl acrylates, with a preference for poly(ethyl acrylate) [9003-32-17, due to its superior balance of properties. The main drawback of these products was the vulcanisation. The fully saturated chemical stmcture of the polymeric backbone in fact is inactive toward the classical accelerators and curing systems. As a consequence they requited the use of aggressive and not versatile compounds such as strong bases, eg, sodium metasiUcate pentahydrate. To overcome this limitation, monomers containing a reactive moiety were incorporated in the polymer backbone by copolymerisation with the usual alkyl acrylates. 

Polymerization processes are characterized by extremes. Industrial products are mixtures with molecular weights of lO" to 10. In a particular polymerization of styrene the viscosity increased by a fac tor of lO " as conversion went from 0 to 60 percent. The adiabatic reaction temperature for complete polymerization of ethylene is 1,800 K (3,240 R). Heat transfer coefficients in stirred tanks with high viscosities can be as low as 25 W/(m °C) (16.2 Btu/[h fH °F]). Reaction times for butadiene-styrene rubbers are 8 to 12 h polyethylene molecules continue to grow lor 30 min whereas ethyl acrylate in 20% emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within hmits. Initiators of the chain reactions have concentration of 10" g mol/L so they are highly sensitive to poisons and impurities. 

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

Strohmeier and Hartmann [14] first reported in 1964 the photoinitiation of polymerization of ethyl acrylate by several transition metal carbonyls in the presence of CCI4. Vinyl chloride has also been polymerized in a similar manner [15,16] No detailed photoinitiation mechanisms were discussed, but it seems most likely that photoinitiation proceeds by the route shown in reaction Scheme (9). 

ESI mass spectrometry ive mass spectrometry ESR spectroscopy set EPR spectroscopy ethyl acetate, chain transfer to 295 ethyl acrylate (EA) polymerizalion, transfer constants, to macromonomers 307 ethyl methacrylate (EMA) polymerization combination v.v disproportionation 255, 262 kinetic parameters 219 tacticity, solvent effects 428 thermodynamics 215 ethyl radicals... 

Using magnesium ether carboxylates as emulsifier a porous polyvinylchloride can be made [218] and a propoxylated ether carboxylate is described as emulsifier to make an ethyl acrylate-styrene copolymer [219]. A crosslinked latex with a three-dimensional network is achieved by polymerizing an ethylenically unsaturated monomer with a reactive saturated monomer using ether carboxylate as emulsifier [220]. 

Hydration of polymeric membranes may be influenced by the chemical identity of the polymers. A hydrophilic polymer has a higher potential to hydrate than a hydrophobic one. Sefton and Nishimura [56] studied the diffusive permeability of insulin in polyhydroxyethyl methacrylate (37.1% water), polyhydroxy-ethyl acrylate (51.8% water), polymethacrylic acid (67.5% water), and cupro-phane PT-150 membranes. They found that insulin diffusivity through polyacrylate membrane was directly related to the weight fraction of water in the membrane system under investigation (Fig. 17). 

Ethyl acrylate CH2 CHCOOC2H5 15 - 1.8- - 1.2 100 Colourless liquid Acrid odour Polymerizes readily, accelerated by heat, light, organic peroxides Irritant... 

The activity of transition metal allyl compounds for the polymerization of vinyl monomers has been studied by Ballard, Janes, and Medinger (10) and their results are summarized in Table II. Monomers that polymerize readily with anionic initiators, such as sodium or lithium alkyls, polymerize vigorously with allyl compounds typical of these are acrylonitrile, methyl methacrylate, and the diene isoprene. Vinyl acetate, vinyl chloride, ethyl acrylate, and allylic monomers do not respond to these initiators under the conditions given in Table II. 

On the basis of the X-ray structural data as well as the mode of polymerization, Yasuda et al. [3a] proposed a coordination anionic mechanism involving an eight membered transition state for the organolanthanide-initiated polymerization of MM A (Fig. 6). The steric control of the polymerization reaction may be ascribed to the intermolecular repulsion between C(7) and C(9) (or the polymer chain), since completely atactic polymerization occurred when the monomer was methyl or ethyl acrylate. 

Standard on Explosion Prevention Systems, National Fire Protection Association, 2002). For example, methyl acrylate and ethyl acrylate are commonly stabilized with hydroquinone monomethyl ether. Industry guidance recommends a minimum concentration of 5 vol % 02 in the atmosphere above the acrylate to prevent polymerization (Intercompany Committee for the Safety and Handling of Acrylic Monomers, Acrylate Esters, A Summary of Safety ana Handling, 3d ed., 2002). 

The ethyl acrylate (60 per cent solution in alcohol) is available from the Rohm and Haas Company. The solution, containing a polymerization inhibitor, is used without treatment. The inhibitor must not be removed. 

Items b and d may be related since the decrease in rate begins to be observed at about 40% conversion, i.e. at the point where [AN] has fallen to about 2.25 M. It is interesting to note that we ( ) and others ( 5) have also noted very slow rates of polymerization of ethyl acrylate at 1 M concentrations in ethyl acetate using either tetrabutyl ammoniurn bromide or 18-crown-6 as the phase transfer catalyst. Further studies in this area are needed. 

Chemical/Physical. Polymerizes on standing and is catalyzed by heat, light, and peroxides (Windholz et al., 1983). Slowly hydrolyzes in water forming ethanol and acrylic acid. The reported rate constant for the reaction of ethyl acrylate with ozone in the gas phase was determined to be 5.70 X 10cm moFsec (Munshi et al., 1989). 

The Wittig-Horner (W-H) reaction is a versatile method for the synthesis of functionalized alkenes. The synthesis of 3-substituted ethyl acrylates and acrylonitriles, which are used as monomers in polymerization, were successfully carried out by the reaction of triethyl phosphonoacetate or cyanomethanephosphonate, respectively, with various aldehydes with activated Ba(OH)2 as the catalyst in the presence of dioxane solvent at 343 K (294). As was observed for other basic solid... 

---