Methyl acrylate, carbon dioxide

Poly(methyl acrylate) carbon dioxide carbon dioxide carbon dioxide chlorodrfluoromethane 1996RIN 1999L02 2003 SHE 1991MEI... 

The combustion of this ester is unusual in that it yields considerable amounts of hydrogen peroxide [97]. Other products include methyl acrylate, carbon monoxide and dioxide, methanol and formaldehyde. There is no low temperature mechanism, and no cool flames have been observed. 

Poly(methyl methacrylate-6-butyl acrylate-6-methyl methacrylate) carbon dioxide and poty(methyl methacrylate) 2014P1N... 

Reactions of the hydrido(hydroxo) complex 2 with several substrates were examined (Scheme 6-14) [6]. The reactions are fairly complicated and several different types of reachons are observed depending on the substrate. Methyl acrylate and small Lewis bases such as CO, P(OMe)3, BuNC coordinate to the five-coordinated complex 2 affording the corresponding six-coordinate complexes. In reactions with the unsaturated bonds in dimethylacetylenedicarboxylate, carbon dioxide, phenylisocyanate indications for the addition across the O-H bond but not across the Os-OH bond were obtained. In reactions with olefins such as methyl vinyl ketone or allyl alcohol, elimination of a water molecule was observed to afford a hydrido metalla-cyclic compound or a hydrido (ethyl) complex. No OH insertion product was obtained. 

Photoelimination of carbon dioxide from the 2-oxazolin-5-one 474 in the presence of methyl acrylate affords the cis- and frans-l-pyrrolines 475 and 476.394 A nitrile ylid is believed to be involved in this and other analogous transformations.395... 

A maximum is found in the ratio of endo- to exo-products versus, density in the Diels-Alder reaction between cyclopentadiene and methyl acrylate in supercritical carbon dioxide (Chfford et al 1997). 

For the Diels-Alder reaction between isoprene and methyl acrylate (see fig. 6.4) in supercritical carbon dioxide at 323 K, the solubility parameter of the activated complex was determined in order to study the nature of the complex and the effect of the solvent on the reaction (Ikushima et al., 1994). 

Hsiao, Y.-L. Maury, E. E. DeSimone, J. M. Mawson, S. M. Johnston, K. P. Dispersion Polymerization of Methyl Methacrylate Stabilized with Poly(l, 1-dihydroperfluorooctyl acrylate) in Supercritical Carbon Dioxide. Macromolecules 1995, 28, 8159-8166. 

Phase behavior studies with poly(ethylene-co-methyl acrylate), poly (ethylene-co-butyl acrylate), poly(ethylene-co-acrylic add), and poly(ethylene-co-methacrylic acid) were performed in the normal alkanes, their olefinic analogs, dimethyl ether, chlorodifluoromethane, and carbon dioxide up to 250 °C and 2,700 bar. The backbone architecture of the copolymers as well as the solvent quality greatly influences the solution behavior in supercritical fluids. The effect of cosolvent was also studied using dimethyl ether and ethanol as cosolvent in butane at varying concentrations of cosolvent, exhibiting that the cosolvent effect diminishes with increasing cosolvent concentrations. 

After a-metalation, methoxyallene was alkylated with bromo silyl ether 47 to afford 48. A second metalation at the terminus of the allene was quenched sequentially with carbon dioxide and methyl iodide to give the corresponding allenic ester. Hydrolysis of the enol ether and equilibration gave solely the (E)-y-keto acrylate 49 in 30% overall yield. Ketalization then provided 16, which had previously been converted to pyrenophorin (9). ° ... 

Hsiao YL, Maury EE, DeSimone JM, Mawson S, Johnston KP. Dispersion polymerization of methyl methacrylate stabilized with poly(l,l-dihydroper-fluorooctyl acrylate) in supercritical carbon dioxide. Macromolecules 1995 28 ... 

Meilchen, M. A., 64, 69, 81, 87, 126, 196, 205, 206, 359, 360 Melhem, G. A., 104 Melting point, 21, 46 Merrill, R. C, 77 Methane, 20, 22, 115 Methane-carbon dioxide system, 48 Methane-ethane, 114 Methane-ethane-octane system, 115-117 Methane-hydrocarbon system, 37 Methane-methanol system, 183, 188 Methane-octane system, 114, 116 Methanol, 102,109, 110 Methanol-methane system, 184 Methyl acrylate, 81, 214, 215, 322 Methyl ethyl ketone (MEK)-water-ethylene system, 76... 

Irradiation of phenyl-2//-azirines in the presence of carbon dioxide leads to the formation of the 3-oxazoline-5-one system121-123 and, in some cases, to the isomeric 2-oxazolin-5-one122 [Eq. (24)1. The azirines serve as incipient nitrile ylides, whose 1,3-dipolar structure permits cycloaddition to the dipolarophile C02123 [Eq. (25)1. The reverse reaction, photolytic extrusion of C02 from pseudoxazolones, is synthetically useful, since the dipolar nitrile ylide thus formed can be trapped with a variety of dipolarophiles. Thus, 2,2,4-triphenyl-3-oxazolin-5-one (48) is readily converted into the stabilized ylide (49)124 [Eq. (26)1, and the use of methyl acrylate,122 acrylonitrile,122 and dimethylacetylene dicarboxy-... 

Figure 1.3-2 Experimental data, shown as points, for the ratio of endo to exo product from the reaction of methyl acrylate and cyclopentadiene in carbon dioxide at 313K, with the curves shows predictions derived from eq (1.3-27).

The separation of the products from the IL catalytic mixture can be performed in various cases by simple decanting and phase separation or by product distillation. In this respect, a continuous-flow process using toluene as extractant has been appHed for the selective Pd-catalyzed dimerization of methyl acrylate in ILs [136]. However, in cases where the products are retained in the IL phase, extraction with supercritical carbon dioxide can be used instead of classical liquid-liquid extractions that necessitate the use of organic solvents, which may result in cross-contamination of products. This process was successfully used in catalyst recycling and product separation for the hydroformylation of olefins employing a continuous-flow process in supercritical carbon dioxide-IL mixtures [137]. Similarly, free and immobilized Candida antarctica lipase B dispersed in ILs were used as catalyst for the continuous kinetic resolution of rac-l-phenylethanol in supercritical carbon dioxide at 120°C and 150°C and 10 Mpa with excellent catalytic activity, enzyme stability and enantioselectivity levels (Fig. 3.5-11). 

Fig. 2.10 Solubility of poly(vinyl acetate) (PVA Mv,= 125 kg/mol) and poly(methyl acrylate) (PMA M =31 kg/mol) in supercritical carbon dioxide. Symbols are experimental data (Rindfleisch et at 1996). Lines are modeling results using the PC-SAFT model [79].

In this section, the polymerization of ethylene and a functional monomer is discussed. For this purpose copolymerization reactions of methyl acrylate (MA) and ethylene using a palladium-based catalyst have been carried out in compressed carbon dioxide at different monomer concentrations and monomer ratios. The incorporation of methyl acrylate and the molecular weight of the polymers have been compared to literature values of polymerizations conducted in dichloromethane. 

I g Catalytic Polymerization of Ol ns in Supercritical Carbon Dioxide Table 8.11 Results of copolymerizations of ethylene and methyl acrylate in compressed carbon dioxide. 

Acrylamide monomer is a white crystal, available commercially as a 50 wt % aqueous solution. Acrylamide monomer can be polymerized to a very-high-molecular-weight (lO -lO g/mole) homopolymer, copolymer, or terpolymer. Polyacrylamide (PAM) is a nonionic polymer. The anionic polyacrylamide species can be obtained from the hydrolysis of the amide (—CONH ) functional group of the homopolymer, or from the copolymerization of acrylamide with an anionic monomer, such as acrylic acid (AA) or 2-acrylamino 2-methyl propane sulfonic acid (AMPS). Acrylamide can be copolymerized with a cationic monomer, such as dimethyl diallylammonium chloride (DMDAAC) or acryloyloxyethyl trimethyl ammonium chloride (AETAC), to form the cationic acrylamide polymer. Acrylamide can simultaneously react with anionic and cationic monomers to form a polyampholyte. The acrylamide homopolymer, copolymers, and terpolymers are synthesized (1-20) by free radicals via solution or emulsion or other polymerization methods. F. A. Adamsky and E. J. Beckman (21) reported the inverse emulsion polymerization of acrylamide in supercritical carbon dioxide. The product classes of acrylamide polymers include liquid, dry, and emulsion. 

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