Acrylic acid methyl methacrylate synthesis

Acrylic Esters. A procedure has been described for preparation of higher esters from methyl acrylate that illustrates the use of an acid catalyst together with the removal of one of the products by azeotropic distillation (112). Another procedure for the preparation of butyl acrylate, secondary alkyl acrylates, and hydroxyalkyl acrylates using -toluenesulfonic acid as a catalyst has been described (113). Alurninumisopropoxide catalyzes the reaction of amino alcohols with methyl acrylate and methyl methacrylate. A review of the synthesis of acryhc esters by transesterification is given in Reference 114 (see... 

Chen et al. prepared fluorinated acrylate resin [55] by solution polymerization of a mixture of 2-(perfluoro-( 1,1 -iti>isopropyl)-2-propenyl)oxy-ethyl methacrylate (POMA), butyl acrylate (BA), methyl methacrylate (MMA), and methacrylic acid (MA) in the co-solvents of ethyl acetate, butyl alcohol, and toluene using AIBN as initiator. First, POMA was synthesized as the starting reactants from the intermediate perfluoro nonene and 2-HEMA. Consequently, a series of fluorinated acrylate resins was synthesized with the same solid content, whereas the fluorine content in mixed monomers was varied at 0%, 5%, 10%, 15%, 20%, and 25%. Films of the novel fluorinated acrylate resin were made by spreading the resin on a clean Petri dish followed by drying at room temperature. Scheme 6.13 shows the synthesis pathway of the fluorinated acrylate resin. 

Liu et al. prepared palladium nanoparticles in water-dispersible poly(acrylic acid) (PAA)-lined channels of diblock copolymer microspheres [47]. The diblock microspheres (mean diameter 0.5 pm) were prepared using an oil-in-water emulsion process. The diblock used was poly(t-butylacrylate)-Wock-poly(2-cinna-moyloxyethyl) methacrylate (PtBA-b-PCEMA). Synthesis of the nanoparticles inside the PAA-lined channels of the microspheres was achieved using hydrazine for the reduction of PdCl2, and the nanoparticle formation was confirmed from TEM analysis and electron diffraction study (Fig. 9.1). The Pd-loaded microspheres catalyzed the hydrogenation of methylacrylate to methyl-propionate. The catalytic reactions were carried out in methanol as solvent under dihydro-... 

The vinyl triflate of Komfeld s ketone has been subjected to Heck reactions with methyl acrylate, methyl methacrylate, and methyl 3-(Af-rerf-butoxycarbonyl-lV-methyl)amino-2-methylenepropionate leading to a formal synthesis of lysergic acid [259]. A similar Heck reaction between l-(phenylsulfonyl)indol-5-yl triflate and dehydroalanine methyl ester was described by this research group [260]. Chloropyrazines undergo Heck couplings with both indole and 1-tosylindole, and these reactions are discussed in the pyrazine Chapter [261], Rajeswaran and Srinivasan described an interesting arylation of bromomethyl indole 229 with arenes [262]. Subsequent desulfurization and hydrolysis furnishes 2-arylmethylindoles 230. Bis-indole 231 was also prepared in this study. 

A further development of the Reppe acrylic acid synthesis is the reaction, described in recent literature, of the noble metal-catalyzed carbonylation of higher acetylenes to give the corresponding acrylic acid derivatives. Thus, for example, the Pd-catalyzed carbonylation of propyne (eq. (10)) in the presence of methanol leads directly to methyl methacrylate [23]. Based on this work. Shell has developed a new production process for methyl methacrylate [24]. The propyne required can be isolated from the product streams from crackers, (cf. Section 2.3.2.3). 

The next most important demand for methyl alcohol is as a raw material in the synthesis of many important organic compounds, including formaldehyde acetic acid chloro-methanes, compounds in which the hydroxyl group and/or one or more hydrogen has been replaced by fluorine, chlorine, bromine, and/or iodine methyl methacrylate, a compound from which acrylic plastics are made methylamines, the source of another important class of plastics, dimethyl terephthalate, the monomer for yet another class of plastics and other products. 

Terbutylazine was another example of a triazine herbicide, which was used for MIP synthesis. In otdet to test the ability of different functional monomers to form strong interactions with terbutylazine, a combinatorial approach was used. Thus, MAA, 2-(trifluoromethyl) acrylic acid (TFMAA), hydroxyethyl methacrylate (HEM), methyl methacrylate (MMA), N-vinyl-a-pytrolidone (NVP) and 4-vinylpytidine (4VP) were used for polymer preparation. In dichloromethane, MAA and TFMAA appeared to be the best monomets able to fotm the terbutilazine-specific functional sites. 

Muller and coworkers prepared disc-like polymer Janus particles from assembled films of the triblock copolymer SBM and, after hydrolysis of the ester groups into methacrylic acid units, used these as Pickering stabilizer in the soap-free emulsion polymerization of styrene and butyl acrylate [111]. Armes and coworkers described the synthesis of PMMA/siUca nanocomposite particles in aqueous alcoholic media using silica nanoparticles as stabilizer [112], extending this method to operate in water with a glycerol-modified silica sol [113, 114]. Sacanna showed that methacryloxypropyltrimethoxysilane [115] in the presence of nanosized silica led to spontaneous emulsification in water, which upon a two-step polymerization procedure afforded armored particles with an outer shell of PMMA [116]. Bon and coworkers demonstrated the preparation of armored hybrid polymer latex particles via emulsion polymerization of methyl methacrylate and ethyl methacrylate stabilized by unmodified silica nanoparticles (Ludox TM O) [117]. Performance of an additional conventional seeded emulsion polymerization step provided a straightforward route to more complex multilayered nanocomposite polymer colloids (see Fig. 14). 

Latex with hydroxyl functionalised cores of a methyl methacrylate/butyl acrylate/2-hydroxyethyl methacrylate copolymer, and carboxyl functionalised shells of a methyl methacrylate/butyl acrylate/methacrylic acid copolymer was prepared by free radical polymerisation. The latex was crosslinked using a cycloaliphatic diepoxide added by three alternative modes with the monomers during synthesis dissolved in the solvent and added after latex preparation and emulsified separately, then added. The latex film properties, including viscoelasticity, hardness, tensile properties, and water adsorption were evaluated as functions of crosslinker addition mode. Latex morphology was studied by transmission electron and atomic force microscopy. Optimum results were achieved by introducing half the epoxide by two-step emulsion polymerisation, the balance being added to the latex either in solution or as an emulsion. 8 refs. 

Several other synthetic methods are also in principle feasible. For example, for the preparation of H-H poly(methyl methacrylate) the cyclopolymerization of meth-acrylic acid derivatives if directed exclusively to the five-membered ring formation (42), and for the preparation of H-H polymers of olefins disubstituted on one carbon atom, the Wurtz synthesis has become feasible. (Eqn. 6,7.)... 

There are numerous examples of typical industrial emulsion polymerization recipes available in the open literature (111,112). A process for the synthesis of a polymer with a 50% methyl methacrylate, 49% butyl acrylate, and 1% methacrylic acid terpolymer at a solids content of 45% is described below ... 

One interesting option is the interaction of polyampholytes with proteins this system has been studied by several authors [64, 65]. Polyampholytes are exclusively firom the industrial synthesis, they are derivatives of the polymethaacrylates such as (a) block polyampholytes with block sequences (dimethyl amino) ethyl methacrylate (cationic residue), methyl methacrylate (neutral, hydrophobic residue), and methacrylic acid (anionic residue) and (b) random polyampholytes of (dimethylamino) ethyl methacrylate, methyl methacrylate, and acrylic acid have... 

Kang, K., Kan, C., Du,Y, and Liu, D. 2005. Synthesis and properties of soap-fi ee poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles prepared by seeded emulsion polymerization. Eur. Polym. 7.41 439-45. 

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