Copper -methacrylic acid complex

The catalyst systems employed are based on molybdenum and phosphorus. They also contain Various additives (oxides of bismuth, antimony, thorium, chromium, copper, zirconium, etc.) and occur in the form of complex phosphomolybdates, or preferably heteropolyacids deposited on an inert support (silicon carbide, a-alumina, diatomaceous earths, titanium dioxide, etc.). This makes them quite different from the catalysts used to produce acrylic acid, which do not offer sufficient activity in this case. With residence times of 2 to 5 s, once-through conversion is better than 90 to 95 per cent, and the molar yield of methacrylic acid is up to 85 to 90 per cent The main by-products formed are acetic add, acetone, acrylic add, CO, C02, etc. The major developments in this area were conducted by Asahi Glass, Daicel, Japan Catalytic Chemical, Japanese Gem, Mitsubishi Rayon, Nippon Kayaku, Standard Oil, Sumitomo Chemical, Toyo Soda, Ube, etc. A number of liquid phase processes, operating at about 30°C, in die presence of a catalyst based on silver or cobalt in alkaline medium, have been developed by ARCO (Atlantic Richfield Co,), Asahi, Sumitomo, Union Carbide, etc. 

The effect of copolymer composition on the rate of the hydroquinone oxidation reaction has been studied using IVI-AA copolymers. Curves of the change of the oxidized hydroquinone concentration as a function of reaction time in the presence of polyampholyte-copper(II) complexes are presented in Fig. 10. An increase in the amount of basic groups in the copolymers leads to an increase in the rate of hydroquinone oxidation. Copolymers in which maleic and methacrylic acids are used as a second comonomer of IVI, exhibit lower activity than IVI-AA. 

Inoue, Kida and Imoto [252] found that the oxidation of unsaturated aldehydes such as cinnamaldehyde and acrolein proceeded much more slowly than did oxidation of the saturated substrates in the presence of copper-iron-polyphthalocyanine. As in the case of the saturated acids the products were a mixture of the peracid and the corresponding carboxylic acid. Other groups have recently investigated the oxidation of unsaturated aldehydes in the presence of metal complexes [253-260]. Methacrylic acid and acetic acid were formed in the copper naphthenate catalyzed oxidation of methacrolein [255]. The oxidation of acrolein to acrylic acid was catalyzed by Co, Ni, Mn and Cu acetates [256]. It was found that at concentrations of acrolein in... 

Aluminoxanes suppressed side reactions involving hydrogen transfer. They also formed cyclic structures with starch, giving copolymers that were coated with crystalline polyethylene. A catalyst composed of dicyclopentadienylzirconium dichloride and trimethylaluminium permitted polymerization of ethylene on starch in a toluene suspension at 60 °C for 2h.2806 Graft copolymerization of methyl methacrylate onto starch was also performed with an acetylacetone-copper(II) complex in trichloroacetic acid.2807 The grafting yield and efficiency were proportional to the initiator concentration up to 7.0 x 10-3 mole/L. 

Iron and copper phthalocyanines catalyze the isomerization of dimethyl maleate to dimethyl fumarate in the vapor phase at 300°C. No catalytic activity was observed in solution (338). Magnesium and zinc phthalocyanines catalyze the polymerization of methyl methacrylate when illuminated (Xm 600 m/i) (197). Manganous phthalocyanine (88) and ferrous phthalocyanine (59) catalyze the aerial oxidation of benzyl alcohol to benzaldehyde. The catalytic oxidation of ascorbic acid, using magnesium and copper derivatives, is light-sensitive (190, 310). a-Tetralin is catalytically oxidized, in the presence of the magnesium, zinc, or iron complexes, to a-tetralone, the reaction being chemiluminescent (60, 61,158,169, 371). The oxidation of luminol to 5-aminophthalazine-l,4-dione, catalyzed by iron phthalocyanine, is also chemiluminescent (61, 345, 361). 

Caprolactone (CL) (Acros, 99%) was dried over calcium hydride at r.t. for 48h and then distilled under reduced pressure. 2-(N,N-dimethylamino)ethyl methaciylate (DMAEMA) (Aldrich, 98%) was deprived of its inhibitor by filtration through a basic alumina column, and depending on samples (see text) dried over calcium hydride at r.t. for 24h and then distilled under reduced pressme. Butane-1,4-diol (Acros, > 99%) was dried over calcium hydride for 48h at r.t. and distilled at 70°C under reduced pressure. Triethylamine (NEts, Fluka, 99%) was dried over barium oxide for 48h at r.t. and distilled under reduced pressure. Copper bromide (CuBr, Fluka, 98%) was purified in acetic acid and recrystallized in ethanol under inert atmosphere until a white powder is obtained. Tin(ll) bis-2-ethyl hexanoate (Sn(Oct)2, Aldrich, 95%), methacrylic anhydride (Aldrich, 94%), N,N-dimethylamino-4-pyridine (DMAP, Acros 99%), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA, Aldrich, 97%), ethyl-2-bromoisobutyrate (E BBr, Aldrich, 98%), N,N-dicyclohexylcarbodiimide (DCC, Acros, 99%), were used as received. Tetrahydrofuran (THF, Labscan, 99%) was dried over molecular sieves (4A) and distilled over polystyryl lithium (PS LC) complex under reduced pressure just before use. Toluene (Labscan, 99%) was dried by refluxing over CaH2. 

The hydrogenation of various a/3-unsaturated acids in the presence of rhodium-phosphine complex catalysts whose ligands are chiral at both phosphorus and carbon gives saturated carboxylic acids with enantiomeric excesses up to 70%. The addition of carbon tetrachloride, catalysed by copper(ll) chloride, to (—)-men thy 1 acrylic and methacrylic esters, followed by hydrolysis, results in /3-tri-chloromethyl derivatives (6) having ca. 50% enantiomeric enrichment at the a-position. ... 

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