- Homopolymerization of methacrylamide by anionic process under effect of Maghnite-Na+ (Algerian MMT)
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The present study describes a new way for synthesis of methacrylamide (MAM) and it's homologue polymethacrylamide (PMAM) under effect of montmorillonite clay (Algerian MMT). The interlayer cation of montmorillonite clay was exchanged with Na + protons (anionic process). Monomer was successfully synthesized by the condensation of ammonia with methacrylic anhydride in bulk (without solvent) and the polymer with increasing anionic catalyst (Mag-Na+) in Tetrahydrofuran THF. Furthermore, the obtained monomer (MAM) and polymer (PMAM) were characterized and confirmed by Infrared Spectroscopy (FT-IR), 1H nuclear magnetic resonance (NMR) spectroscopy and Thermal properties by thermogravimetric analysis (TGA). The conversion and yield of monomer-polymer increased with the increase of the amount of catalyst “Maghnite-Na+”, the reactivity of the ammonia related to its basicity and the effect of amine substitution with methacrylic anhydride involved electron donor forces of the substitution group.
- Derkaoui, Samira,Belbachir, Mohammed,Haoue, Sara,Zeggai, Fatima Zohra,Rahmouni, Abdelkader,Ayat, Moulkheir
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Read Online
- Comparison between the electric conductivity of polyhydroxamic acids of different origin
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Polyhydroxamic acid (PHA) was prepared from polyacrylamide (PAA) and from polymethacrylamide (PMAA). It was found that PHA from PAA has the properties of a semiconductor when it reacts with some metals. PHA from PMAA has typical semiconducting properties when reacting with 1 mmol of ferric chloride, whereas its electric conductivity is somewhat lower when it contains 0.5 mmol of ferric chloride.
- Sayed, Wafaa M.,Abed, Yahia M.,Gad, El-Shafie A.M.,Salem, Tousson A.
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Read Online
- Study on the degradation mechanism and pathway of benzene dye intermediate 4-methoxy-2-nitroaniline: Via multiple methods in Fenton oxidation process
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Benzene dye intermediate (BDI) 4-methoxy-2-nitroaniline (4M2NA) wastewater has caused significant environmental concern due to its strong toxicity and potential carcinogenic effects. Reports concerning the degradation of 4M2NA by advanced oxidation process are limited. In this study, 4M2NA degradation by Fenton oxidation has been studied to obtain more insights into the reaction mechanism involved in the oxidation of 4M2NA. Results showed that when the 4M2NA (100 mg L-1) was completely decomposed, the TOC removal efficiency was only 30.70-31.54%, suggesting that some by-products highly recalcitrant to the Fenton oxidation were produced. UV-Vis spectra analysis based on Gauss peak fitting, HPLC analysis combined with two-dimensional correlation spectroscopy and GC-MS detection were carried out to clarify the degradation mechanism and pathway of 4M2NA. A total of nineteen reaction intermediates were identified and two possible degradation pathways were illustrated. Theoretical TOC calculated based on the concentration of oxalic acid, acetic acid, formic acid, and 4M2NA in the degradation process was nearly 94.41-97.11% of the measured TOC, indicating that the oxalic acid, acetic acid and formic acid were the main products. Finally, the predominant degradation pathway was proposed. These results could provide significant information to better understand the degradation mechanism of 4M2NA.
- Guo, Ying,Xue, Qiang,Cui, Kangping,Zhang, Jia,Wang, Hui,Zhang, Huanzhen,Yuan, Fang,Chen, Honghan
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p. 10764 - 10775
(2018/03/26)
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- Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(ii) complexes
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The (PCP)Ni-OH complexes 2R (R = iPr, tBu, Cy) are effective catalyst precursors for the selective hydration of nitriles to the corresponding amides under relatively mild conditions (80 °C) and low catalyst loadings (0.05-0.5%). Substrate scope includes aliphatic, vinylic and aromatic nitriles, but substrates with protic groups poison the catalyst abruptly. The catalysts are effective because the electron rich nature of the PCP ligands and their steric bulk renders the hydroxo group labile.
- Borau-Garcia,Gutsulyak,Burford,Piers
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p. 12082 - 12085
(2016/01/15)
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- Synthesis and Structural Characterization of Nickel Complexes Possessing P-Stereogenic Pincer Scaffolds and Their Application in Asymmetric Aza-Michael Reactions
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Novel P-stereogenic pincer-Ni complexes {κP,κC,κP-3,5-Me2-2,6-(MetBuPCH2)2C6H}NiCl (3), {κP,κC,κP-3,5-Me2-2,6-(MetBuPCH2)2C6H}NiOTf (4), [{κP,κN,κP-2,6-(MetBuPCH2)2C5H3N}NiCl]Cl (7), [{κP,κN,κP-2,6-(MetBuPCH2)2C5H3N}NiCl]BF4 (8), and [{κP,κN,κP-2,6-(MetBuPCH2)2C5H3N}Ni(NCMe)](BF4)2 (9) were synthesized in 55-84% yields and characterized by 1H NMR, 13C{1H} NMR, 31P{1H} NMR, 19F{1H} NMR, and/or single-crystal X-ray diffractions. The ORTEP diagrams of complexes 3, 7, 8, and 9 show that the coordination geometries around the Ni center in all these structures are approximately square planar but have different bond lengths and angles. These complexes were shown to be active catalysts for the asymmetric aza-Michael addition of α,β-unsaturated nitriles. For most examples good to excellent yields (up to 99%) and moderate enantiomeric excesses (up to 46% ee) were obtained. Notably, the PCP complex 3 exhibited higher catalytic activity in the aza-Michael addition than the PNP complexes 7, 8, and 9. Two achiral PCP-type pincer-Ni complexes, {κP,κC,κP-3,5-Me2-2,6-(tBu2PCH2)2C6H}NiCl (11) and {κP,κC,κP-3,5-Me2-2,6-(Ph2PCH2)2C6H}NiCl (13), were also synthesized and fully characterized in order to reveal the structural differences between the chiral and achiral complexes. (Chemical Equation Presented).
- Yang, Zehua,Liu, Delong,Liu, Yangang,Sugiya, Masashi,Imamoto, Tsuneo,Zhang, Wanbin
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supporting information
p. 1228 - 1237
(2015/04/27)
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- Metal complex compound and process for producing amides utilizing the metal complex compound
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A catalyst contains a metal complex compound represented by the following general formula (I). In the formula (I), M is a metal ion such as ruthenium, L1 is a cyclic or acyclic, neutral or minus 1-valent unsaturated hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, L2 and L3 are each independently chlorine or the like, and L4 is a compound bonded to M through phosphorus or arsenic and represented by the following general formula (IIa) or (IIb). In the formulas (IIa) and (IIb), E is phosphorus or arsenic, Y1 is oxygen or sulfur, Y2, Y3 and Y4 are each independently a hydrogen atom, an aryl group or the like, and H is a hydrogen atom.
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Page/Page column 27
(2014/05/20)
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- Catalytic nitrile hydration with [Ru(η6- p -cymene)Cl 2(PR2R′)] complexes: Secondary coordination sphere effects with phosphine oxide and phosphinite ligands
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The rates of nitrile hydration reactions were investigated using [Ru(η6-p-cymene)Cl2(PR2R′)] complexes as homogeneous catalysts, where PR2R′ = PMe 2(CH2P(O)Me2), PMe2(CH 2CH2P(O)Me2), PPh2(CH 2P(O)Ph2), PPh2(CH2CH 2P(O)Ph2), PMe2OH, P(OEt)2OH. These catalysts were studied because the rate of the nitrile-to-amide hydration reaction was hypothesized to be affected by the position of the hydrogen bond accepting group in the secondary coordination sphere of the catalyst. Experiments showed that the rate of nitrile hydration was fastest when using [Ru(η6-p-cymene)Cl2PMe2OH]: i.e., the catalyst with the hydrogen bond accepting group capable of forming the most stable ring in the transition state of the rate-limiting step. This catalyst is also active at pH 3.5 and at low temperatures - conditions where α-hydroxynitriles (cyanohydrins) produce less cyanide, a known poison for organometallic nitrile hydration catalysts. The [Ru(η6-p-cymene) Cl2PMe2OH] catalyst completely converts the cyanohydrins glycolonitrile and lactonitrile to their corresponding α-hydroxyamides faster than previously investigated catalysts. [Ru(η6-p-cymene) Cl2PMe2OH] is not, however, a good catalyst for acetone cyanohydrin hydration, because it is susceptible to cyanide poisoning. Protecting the -OH group of acetone cyanohydrin was shown to be an effective way to prevent cyanide poisoning, resulting in quantitative hydration of acetone cyanohydrin acetate.
- Knapp, Spring Melody M.,Sherbow, Tobias J.,Yelle, Robert B.,Juliette, J. Jerrick,Tyler, David R.
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supporting information
p. 3744 - 3752
(2013/07/26)
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- Cyclization of the semicarbazones to 1,3,4-oxadiazole derivatives using ceric ammonium nitrate as oxidant
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Cyclization of the semicarbazones to 1,3,4-oxadiazole using ceric ammonium nitrate as oxidant was studied. 2-Imino-1,3,4-oxadiazolines can be produced from semicarbazones, which undergo thermolysis to amides. Benzoic acid benzylidene hydrazide can also be cyclized to 2-methoxy-2-phenyl-1,3,4-oxadiazole in the presence of ceric ammonium nitrate and methanol.
- Vahedi,Lari,Bavand,Ameri
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experimental part
p. 288 - 290
(2012/08/08)
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- A general and efficient heterogeneous gold-catalyzed hydration of nitriles in neat water under mild atmospheric conditions
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Mild, efficient and general: Titania decorated with nanometer-sized gold particles acts as an efficient catalyst for the selective hydration of a wide range of chemically diverse nitriles into valuable amides in neutral water, under mild atmospheric conditions (see image). The process shows promise for a facile and direct one-pot synthesis of ?μ-caprolactam, an industrially important molecule, starting from 6-aminocapronitrile. Copyright
- Liu, Yong-Mei,He, Lin,Wang, Miao-Miao,Cao, Yong,He, He-Yong,Fan, Kang-Nian
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scheme or table
p. 1392 - 1396
(2012/10/07)
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- Natural kaolin supported sulfuric acid as an efficient catalyst for selective hydrolysis of nitriles to amides
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The natural kaolin supported sulfuric acid as an efficient catalyst for selective hydrolysis of nitriles to amides was investigated. The nitrile (4 mmol) was dissolved in water (10 mL) in the presence of kaolin and refluxed for 24 h. The crude product was extracted with ethyl acetate in 55-80% yields after completion of the reaction (monitored by TLC). Careful neutralization of all reaction mixtures were carried out to pH = 7 for exact monitoring of reaction for possible formation of carboxylic acid. The products were characterized by IR and 1H NMR spectroscopy and also their melting points are compared with authentic samples. The disappearance of one strong and sharp absorption band (CN stretching band), and the appearance of two NH2 stretching bands in 3370 and 3320 cm-1 and carboxamide stretching in 1650 cm-1 in the IR spectra, were evidence for the formation of primary amides.
- Gordi, Zinat,Eshghi, Hossein
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experimental part
p. 715 - 718
(2011/10/08)
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- RhI-catalyzed hydration of organonitriles under ambient conditions
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(Chemical Presented) New scoop on scope and selectivity: The hydration of organonitriles catalyzed by a RhI(OMe) species under nearly pH-neutral and ambient conditions (25°C, 1 atm) is chemoselective and high-yielding (93 to 99%), has a broad substrate scope, and may thus be complementary to enzymatic hydration methods for the introduction of a terminal amido group (CONH2) onto a carbon chain.
- Goto, Akihiro,Endo, Kohei,Saito, Susumu
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p. 3607 - 3609
(2008/12/23)
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- Process for chemical reactions involving cyanohydrins
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The present invention provides a method for minimizing the decomposition of cyanohydrins in exothermic chemical reactions involving cyanohydrins. The method comprises providing a reaction medium and reactants to a tubular reactor having internal mixing means, mixing the reaction medium and reactants to form a homogenous reaction mixture, removing heat from the reaction process and reacting the reactants to produce a mixed product having a bulk temperature. The method may further comprise cooling the reaction medium to a temperature from 1-10° C. cooler than the bulk temperature of the mixed product prior to providing the reaction medium to the tubular reactor.
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Page/Page column 5-6; 8
(2008/06/13)
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- PRODUCTION OF AMIDES AND/OR ACIDS FROM NITRILES
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A process for producing an amide and/or acid from a nitrile comprises introducing a nitrile, as a first reactant, and a hydration compound, as a second reactant which is capable of reacting with the nitrile to convert it to its corresponding amide thus hydrating the nitrile and/or to convert it to its corresponding acid, into a treatment zone. The nitrile is subjected to catalytic distillation in the treatment zone in the presence of the hydration compound, to hydrate at least some of the nitrile to the corresponding amide and/or to form its corresponding acid. The amide and/or acid is withdrawn from the treatment zone.
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- Water soluble polymer composition and method of use
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Novel water soluble polymers in solution or water-in-oil emulsion form are disclosed containing quaternary ammonium monomers; and optionally (meth)acrylic acid or 2-(meth)acrylamido-2-methylpropane sulfonic acid; methylene bis-acryamide and the like; and a C1-C3alkyl (meth) acrylate acrylamide or methacrylamide and the use thereof in hair, skin and nail conditioning; papermaking; and subterranean well drilling and well cementing operations.
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- RhCl3-catalyzed hydroboration of alkenyl nitriles
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RhCl3-promoted hydroboration-oxidation reactions of representative alkenyl nitriles have been carried out. Carbanion of acetonitrile is formed from the carbon-carbon heterolytic bond breaking in allyl cyanide during hydroboration. An unexpected process-trimerization of carbanion of acetonitrile has lead to the formation of 4-amino-2,6-dimethylpyrimidine.
- Buranov, Anvar U.,Morrill, Terence C.
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p. 6301 - 6304
(2007/10/03)
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- POLYMERIZABLE BIOTIN DERIVATIVES, BIOTIN POLYMER, AND POLYMER RESPONSIVE TO AVIDIN STIMULATION
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The present invention is to prepare a novel polymerizable biotin derivative represented by formula (I) shown below and make it possible to synthesize or design a polyfunctional or multifunctional polymer using the derivative. In formula (I), R2 represents a hydrogen atom or an alkyl grouo, R3 and R4 each independently represents a hydrogen atom, an alkyl group or an aryl group, T represents an oxygen atom or =NH, W represents a single bond, a carbonyl group, a thiocarbonyl group or a C1-5 alkylene group, U represents a single bond or -NH-, X represents a single bond, a C1-8 hydrocarbon bond, an oxygen atom or -NH-, Y represents a single bond, a carbonyl group, a thiocarbonyl group, -NH-, a 1,2-dioxyethylene group or a 1,2-diaminoethylene group, Z represents a single bond, a carbonyl group, a thiocarbonyl group, a C1-5 alkylene group, an oxygen atom or -NH-, and V represents a single bond or a C1-5 alkylene group.
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- Monomeric and polymeric cyclic amine and N-halamine compounds
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Cyclic amine monomers and polymers and N-halamine biocidal polymer compounds are provided. Methods of making and using the same wherein the functional groups unhalogenated or halogenated hydantoins, triazine diones, imidazolidinones, and pyrimidinones are substituted onto inexpensive polymer units such as polystyrene, polyethylene, and modified polymethacrylamide are provided. The cyclic amine monomers and polymers can be utilized to form the biocidal N-halamine polymers. These N-halamine polymers are stable, insoluble biocides which release only small amounts of free halogen and other impurities. They can be useful as disinfectants for potable water, swimming pools, hot tubs, industrial water systems, cooling towers, air-conditioning systems, gas streams, paints, oils, ointments, fabrics, rubber materials, sterile bandages, coatings, hard surfaces, liners of containers, and the like.
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- An in-depth study of the biotransformation of nitriles into amides and/or acids using Rhodococcus rhodochrous AJ270
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A variety of aliphatic, aromatic and heterocyclic nitriles have been readily hydrolysed into the corresponding amides and/or acids under very mild conditions using Rhodococcus sp. AJ270. The nitrile hydratase involved in this novel nitrile-hydrolysing microorganism efficiently hydrates most nitriles tested, irrespective of the electronic and steric effects of the substituents, to form the amides. Conversion of amides into acids catalysed by the associated amidase is rapid and efficient in most cases. Substrates bearing an adjacent substituent (which may be an ortho substituent on an aromatic nitrile, an adjacent heteroatom in a heterocyclic ring or a geminal substituent in an α,β-unsaturated nitrile) undergo slow hydrolysis of the amides allowing efficient amide isolation. The scope, limitations and reaction mechanism of this enzymatic process have been systematically studied. A molecular size of >7 A diameter and the presence of functions capable of metal complexation near to the nitrile inhibit hydrolysis.
- Meth-Cohn, Otto,Wang, Mei-Xiang
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p. 1099 - 1104
(2007/10/03)
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- Polymeric cyclic N-halamine biocidal compounds
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Cyclic N-halamine biocidal polymer compounds and methods of using the same wherein the functional groups halogenated hydantoins, triazine diones, imidazolidinones, and pyrimidinones are substituted onto inexpensive polymer units such as polystyrene, polyethylene, and modified polymethacrylamide are provided. These N-halamine polymers are stable, insoluble biocides which release only small amounts of free halogen and other impurities. They will be useful as disinfectants for potable water, swimming pools, hot tubs, industrial water systems, cooling towers, air-conditioning systems, gas streams, paints, oils, ointments, fabrics, sterile bandages, coatings, hard surfaces, liners of containers, and the like.
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- Purification process of methacrylamide
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A purification process of crude methacrylamide by recrystallization from an aqueous methacrylamide solution, comprising the steps of conducting crystallization by adjusting the hydrogen ion concentration of the aqueous methacrylamide solution to pH 8 or more, separating a methacrylamide crystal, adjusting 5% by weight or more of resulting mother liquor to pH 5 or less, separating precipitated insoluble matter, and reusing thus-treated mother liquor, is provided. The high quality methacrylamide crystal thus obtained is excellent in Hazen number, purity and transparency of a methanol solution and suitable for uses such as windshield glasses.
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- Kinetics and Mechanism of the Formation of Methacrylamide from 2-Methyl-2-sulphatopropionamide in Strong Acid Media
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The kinetics and mechanism of the elimination of sulphuric acid from the sulphate ester of 2-hydroxy-2-methylpropionamide in 90-102percent H2SO4 have been studied by multinuclear (1H, 2H, 13C and 15N) NMR spectroscopy.The results, which include activation parameters, influence of acid strength and kinetic isotope effects, are consistent with an E2 elimination occurring from the protonated substrate and involving the hydrogensulphate anion as a base.
- Hall, C. Dennis,Leeding, Christopher J.,Jones, Stephen,Case-Green, Stephen,Sanderson, Ian,Hoorn, Marielle van
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p. 417 - 422
(2007/10/02)
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- Process for the acrylamidoacylation of alcohols
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The present invention provides a dramatically improved process for the preparation of acrylamide and methacrylamide functional monomers, oligomers, and polymers that avoids the use of acidic catalysts which can cause undesired side reactions. The present invention process involves reacting an alkenyl azlactone with a hydroxy functional compound in the presence of a catalytic amount of either a bicyclic amidine or a trivalent phosphorus compound. These efficient basic catalysts provide unexpectedly increased reaction rates under mild conditions.
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- Anhydrous nail lacquer containing as a resin a copolymer comprising units of vinylsulfonamide or a unsaturated amide and of an alkyl acrylate or methacrylate
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Nail lacquer compositions comprising a polymer resin consisting essentially of units resulting from the copolymerization of: (1) 75 to 97% by weight of at least one monomer having the general formula: STR1 in which: R1 represents an hydrogen atom or a methyl radical, and R2 represents a linear alkyl radical or a branched radical having 1 to 18 carbon atoms, a mono or dihydroxy alkyl radical, the alkyl radical having from 2 to 4 carbon atoms, a glycidyl radical or the radical --(CH2)n --OR', wherein R' represents methyl or ethyl and n is 3 or 4, and (2) 3 to 25% by weight of at least one monomer selected from the group consisting of N-vinylsulfonamide, 4-styrenesulfonamide, acrylamide, methacrylamide, N-(N'N',3-dimethylaminopropyl) methacrylamide and N-(N'N',3-dimethylaminopropyl) acrylamide.
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- Process for purifying methacrylamide
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In a conventional process for the purification of crude methacrylamide by the recrystallization from an aqueous medium, pH of the aqueous methacrylamide solution is controlled to a value in alkaline range of at least 8 and then methacrylamide is crystallized out. As the alkali used for the pH control, there have been used alkali metal and alkaline earth metal carbonates and hydroxides. Methacrylamide to be recrystallized is crude methacrylamide obtained by neutralizing methacrylamide sulfate obtained from acetone cyanhydrin and sulfuric acid with ammonia in the presence of water.
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- Process for the preparation of methacrylamide from methylmethacrylate
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This invention relates to an improved process for the preparation of methacrylamide by the reaction of methylmethacrylate with a molar excess of aqueous ammonium hydroxide at or near ambient temperatures to provide a high purity and yield of methacrylamide reaction product that is compatible in the preparation of isocyanate resins. Optional surfactants and alkoxide catalysts may be utilized to increase the rate of the reaction of methylmethacrylate with ammonia which may be further fostered by the addition of gaseous ammonia to the aqueous ammonium hydroxidemethylmethacrylate reaction mixture to yield methacrylamide according to the general equation: STR1
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- Conformational Analysis of Some Acrylamide Homologues
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UV absorption and 13C NMR spectra of some acrylamide homologues are discussed in terms of their conformations.They usually assume the planar s-cis conformations, but steric effects in N,N-dimethylamides of methacrylic and senecioic acids are shown to force the molecules into non-planar structures.
- Wojcik, Jacek,Szymanski, Slawomir,Witanowski, Michal,Stefaniak, Lech
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p. 613 - 619
(2007/10/02)
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- Process for the production of acrylamide and methacrylamide
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Process for the production of acrylamide or methacrylamide wherein acrylonitrile or methacrylonitrile is reacted with water and/or water donor in the presence of a catalyst consisting essentially of Raney copper, Ullman copper, reduced copper catalyst, copper with a carrier, silver, gold, cobalt, palladium and/or platinum.
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