- A Kinetic Study of Poly(acrylic acid)-Copper(II) Interactions in Aqueous Solutions
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Concentration-jump kinetic studies of the aqueous poly(acrylic acid)-copper(II) system reveal the presence of a relaxation phenomenon in the time range of 102 ms.Kinetic data under various pH's and compositions, together with the potentiometric results, indicate that this relaxation effect is due to the following complex-formation reaction: where L23- is a coordination unit consisting of two adjacent carboxylato side groups on the polymer chain.The specific features of the pH dependence of the τ-1 value are discussed in relation to the degree of dissociation of the carboxyl groups.The rate and stability constants of the reaction are determined to be: k2 = 5.6 * 103 M-1 s-1 (1M = 1 mol dm-3), k-2 = 0.7 s-1, and K2 (=k2/k-2) = 7.9 * 103, at pH 7.0, I ca. 0, and 25 deg C.The overall complex-formation mechanism, involving the very rapid formation of CuL2, is discussed.
- Yamada, Ryuichi,Tamura, Kiyoshi,Harada, Shoji,Yasunaga, Tatsuya
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Read Online
- Synthesis and Reactivity of 1,2-Bis(di- iso-propylphosphino)benzene Nickel Complexes: A Study of Catalytic CO2-Ethylene Coupling
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The utilization of renewable carbon dioxide resources in the production of commercial chemicals has been at the center of efforts to improve the sustainability of many widely used consumer products. The catalytic coupling of CO2 with ethylene to generate acrylates is one such avenue of research. Despite decades of investigations, catalytic CO2-ethylene coupling has only recently been experimentally demonstrated. The development of a new nickel-based catalyst, 1,2-bis(di-iso-propylphosphino)benzene nickel(0) 1,5-cyclooctadiene, for acrylate production is detailed here. The stoichiometric reactivity of the catalyst toward the CO2, ethylene, and base reagents, as well as the coordination chemistry of likely catalytic intermediates has been examined. Comparative catalytic experiments were used to identify the influence of commonly employed additives, such as metallic zinc and Lewis acidic salts, on the catalytic CO2-ethylene coupling reaction. In addition, catalytic comparisons of the 1,2-bis(di-iso-propylphosphino)benzene nickel(0) 1,5-cyclooctadiene species with a similar previously reported catalyst under newly developed conditions afforded turnover numbers greater than 400, an approximately 4-fold increase over the highest activity reported to date. Significantly, the catalytic trials reveal that small changes in the catalytic conditions and additives can have substantial effects on productivity and that these influences are not uniform with respect to catalyst platforms.
- Hopkins, Melissa N.,Shimmei, Kenichi,Uttley, Katherine B.,Bernskoetter, Wesley H.
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Read Online
- Vinyl monomers-induced synthesis of polyvinyl alcohol-stabilized selenium nanoparticles
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A simple wet chemical method has been developed to synthesize selenium nanoparticles (size 100-200 nm), by reaction of sodium selenosulphate precursor with different vinyl monomers, such as acrylamide, N,N′-dimethylene bis acrylamide, methyl methacrylate, sodium acrylate, etc., in aqueous medium, under ambient conditions. Polyvinyl alcohol has been used to stabilize the selenium nanoparticles. Average size of the synthesized selenium nanoparticles can be controlled by adjusting concentration of both the precursors and the stabilizer. Rate of the reaction as well as size of the resultant selenium nanoparticles have been correlated with the functional groups of the different monomers. UV-vis optical absorption spectroscopy, X-ray diffraction, energy dispersive X-rays, differential scanning calorimetry, atomic force microscopy, scanning electron microscopy and transmission electron microscopy techniques have been employed to characterize the synthesized selenium nanoparticles. Gas chromatographic analysis of the reaction mixture established the non-catalytic role of the vinyl monomers, which were found to be consumed during the course of the reaction.
- Shah, Chetan P.,Singh, Krishan K.,Kumar, Manmohan,Bajaj, Parma N.
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Read Online
- Copolymerization of sodium acrylate with new acrylamide derivatives in the presence of water-soluble salts
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Copolymerization of sodium acrylate with new acrylamide derivatives was studied. The copolymerization constants r1 and r2 of the monomers and the molecular weights of the copolymers were determined.
- Eritsyan,Barsegyan, Zh. B.,Manukyan, Sh. M.,Karapetyan
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Read Online
- Ancillary Ligand and Base Influences on Nickel-Catalyzed Coupling of CO2 and Ethylene to Acrylate
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The coupling of CO2 and ethylene to produce acrylates has been an area of increasing interest in recent years following a number of studies which have empirically improved catalytic turnover. Notably, the incorporation of moderately Br?nsted and Lewis basic sodium phenoxide salts, as well as zinc dust, and Lewis acidic lithium salts were found to facilitate acrylate formation in batch catalysis. Despite these advances, there has been limited investigation into the effect of the catalyst ancillary ligand and phenoxide base structure on catalytic performance. Here, a collection of 1,2-bis(dialkylphosphino)benzene and related diphosphine ligands were used to show that the influence of steric environs has a marked effect on turnover. Ancillary diphosphine ligands featuring at least two smaller alkyl substituents are needed for strong activity, while the oft-used benzene annulation of the diphosphine does not appear to be determinant in achieving high turnover values. Additionally, the investigation of a collection of substituted sodium phenoxide bases suggests that a subtle balance of basicity and steric factors must be satisfied to obtain optimal catalytic performance. These trends appear to result from competitive, deleterious nucleophilic reactions between base and CO2 to produce carbonate and the need to maintain sufficient basicity and access to the metal coordination sphere to drive the endergonic CO2-ethylene coupling reaction.
- Uttley, Katherine B.,Shimmei, Kenichi,Bernskoetter, Wesley H.
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Read Online
- Palladium- and Nickel-Catalyzed Synthesis of Sodium Acrylate from Ethylene, CO2, and Phenolate Bases: Optimization of the Catalytic System for a Potential Process
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The synthesis of sodium acrylate through catalytic carboxylation of ethylene with CO2 in the presence of a base is a reaction of high interest. To develop a more efficient and sustainable method to access this valuable acrylate monomer, we optimized the system in a one-step homogeneous nickel- or palladium-catalyzed reaction, without the need for stoichiometric amounts of an additional reducing agent. Suitable nontoxic solvents such as anisole instead of the previously reported tetrahydrofuran or chlorobenzene were found to lead to acrylate formation. In combination with appropriate phenolate bases, this could allow a rational process concept for a simple catalyst recycling, product separation, and base regeneration. The carboxylation of ethylene with CO2 in the presence of phenolate bases to give sodium acrylate was improved to develop the basis for a continuous process concept. The homogeneous nickel- or palladium-catalyzed transformation does not require stoichiometric reductants, and appropriate solvents as well as bases were identified that are suitable for a first recycling protocol.
- Manzini, Simone,Huguet, Núria,Trapp, Oliver,Schaub, Thomas
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Read Online
- Highly Efficient Biobased Synthesis of Acrylic Acid
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Petrochemical based polymers, paints and coatings are cornerstones of modern industry but our future sustainable society demands greener processes and renewable feedstock materials. A challenge is to access platform monomers from biomass resources while integrating the principles of green chemistry in their chemical synthesis. We present a synthesis route starting from biomass-derived furfural towards the commonly used monomers maleic anhydride and acrylic acid, implementing environmentally benign photooxygenation, aerobic oxidation and ethenolysis reactions. Maleic anhydride and acrylic acid, transformed into sodium acrylate, were isolated in yields of 85 % (2 steps) and 81 % (4 steps), respectively. With minimal waste and high atom efficiency, this biobased route provides a viable alternative to access key monomers.
- Feringa, Ben L.,Hermens, Johannes G. H.,Jensma, Andries
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supporting information
(2021/12/16)
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- CATALYTIC PROCESS FOR PREPARING AN α,β-ETHYLENICALLY UNSATURATED CARBOXYLIC ACID SALT
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A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising a) contacting an alkene and carbon dioxide with a carboxylation catalyst, an organic solvent, and an alkoxide having a secondary or tertiary carbon atom directly bound to an [O-] group, to obtain a crude reaction product comprising the α,β-ethylenically unsaturated carboxylic acid salt and an alcohol by-product which is the conjugate acid of the alkoxide, b) allowing the α,β-ethylenically unsaturated carboxylic acid salt to precipitate out from the crude reaction product; and c) subjecting at least part of the crude reaction product to a mechanical separation step while maintaining the alcohol by-product in liquid form to obtain a solid phase comprising the α,β-ethylenically unsaturated carboxylic acid salt and a liquid phase comprising the carboxylation catalyst, the organic solvent and the alcohol by-product. The process allows for easy separation of the α,β-ethylenically unsaturated carboxylic acid salt by a mechanical separation operation.
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Page/Page column 31-34
(2021/09/26)
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- Powder composition for pack and manufacturing method thereof, microgel for sherbet-shaped beauty pack utilizing the powder composition, and manufacturing method thereof
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The present invention relates to a powder composition for a pack, a method for manufacturing the same, sherbet-type microgel for a cosmetic pack using the powder composition, and a method for manufacturing the microgel. More specifically, the present invention relates to: a powder composition for a pack which has excellent swelling properties and elastic modulus, exhibits appropriate viscosity, has excellent adsorption and moisturizing power, and at the same time, exhibits an excellent cooling effect; a method or manufacturing the same; sherbet-type microgel for a cosmetic pack using the powder composition; and a method for manufacturing the microgel.
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Paragraph 0028; 0075-0076
(2021/01/28)
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- METHODS OF PRODUCING ALPHA, BETA-UNSATURATED CARBOXYLIC ACID SALTS FROM ALKANES AND CARBON DIOXIDE
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Methods of producing α,β-unsaturated carboxylic acid salt are described. A method can include reacting an alkene and carbon dioxide with a composition that includes a carboxylation catalyst, an organic base that is solubilized in the composition, and an inorganic base that is not solubilized in the composition, under reaction conditions suitable to produce an inorganic base salt of an α,β-unsaturated carboxylic acid. The organic base can have a first pKa and the inorganic base has a second pKa that is greater than the first pKa.
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Paragraph 0068-0069
(2019/04/11)
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- Development of N-Phosphinomethyl-Substituted NHC-Nickel(0) Complexes as Robust Catalysts for Acrylate Salt Synthesis from Ethylene and CO2
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By using a nickel complex with an N-phosphinomethyl-N-heterocyclic carbene ligand (NHC-P), the reducing ability and thermal stability of the complex were improved considerably compared to the previously reported bipyridine and bisphosphine complexes, and acrylate salt was prepared from ethylene and CO2 with the highest TON ever reported for nickel systems even without using metallic zinc. Oxidative cyclization of ethylene and CO2 on the NHC-P nickel complex was found to proceed very rapidly compared to previous systems.
- Takahashi, Kohei,Cho, Kinryo,Iwai, Asaki,Ito, Tatsuyoshi,Iwasawa, Nobuharu
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supporting information
p. 13504 - 13508
(2019/10/28)
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- Simple method for preparing 3-methylthiopropionic acid
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The invention relates to a simple method for preparing 3-methylthiopropionic acid. The method comprises taking acrylic acid and sodium methyl mercaptide as raw materials for reaction in alkaline aqueous solution at 30-60 DEG C for 2-5, performing acidification by concentrated sulfuric acid and extraction by organic solvent to separate out organic phase, and performing normal-temperature distillation to recover the solvent and reduced-pressure distillation to obtain the 3-methylthiopropionic acid. The simple method for preparing the 3-methylthiopropionic acid is low in cost, simple in operation, high in yield and purity of prepared products and applicable to industrial production.
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Paragraph 0013; 0015; 0017
(2019/05/02)
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- CONTINUOUS PROCESS FOR THE CONVERSION OF OLEFINS AND CARBON DIOXIDE TO ACRYLATES VIA SOLUTION PHASE REACTOR
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Disclosed is a continuous process for producing α,β-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO2), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an α,β-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.
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Paragraph 0208
(2019/01/04)
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- A family of cis-macrocyclic diphosphines: modular, stereoselective synthesis and application in catalytic CO2/ethylene coupling
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A family of cis-macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene, or P2(dmb)2, produced phosphino-phosphonium salts [R-P2(dmb)2]X, where R is methyl, benzyl and isobutyl, in yields of 90-96%. Treatment of these salts with organolithium or Grignard reagents yielded symmetric and unsymmetric macrocyclic diphosphines of the form cis-1-R-6-R′-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R′-DPC, in which R′ is methyl, cyclohexyl, phenyl or mesityl, in yields of 46-94%. Alternatively, symmetric diphosphine Cy2-DPC was synthesized in 74% yield from the dichlorodiphosphine Cl2P2(dmb)2. As a first application, these cis-macrocyclic diphosphines were used as ligands in the nickel-catalyzed synthesis of acrylate from CO2 and ethylene, for which they showed promising catalytic activity.
- Knopf, Ioana,Tofan, Daniel,Beetstra, Dirk,Al-Nezari, Abdulaziz,Al-Bahily, Khalid,Cummins, Christopher C.
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p. 1463 - 1468
(2017/02/10)
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- PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT
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The present invention relates to a catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising contacting an alkene and carbon dioxide with a carboxylation catalyst being a transition metal complex, an alkoxide, and an organic solvent, to obtain an α,β-ethylenically unsaturated carboxylic acid salt, the organic solvent being incompletely miscible with water at a pressure of 1 bar at at least one temperature T and selected from amides and ureas, T being a temperature in the range from 10°C to 90°C.
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Page/Page column 41; 42; 44
(2017/11/10)
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- Enhanced Activity and Recyclability of Palladium Complexes in the Catalytic Synthesis of Sodium Acrylate from Carbon Dioxide and Ethylene
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The Pd-catalysed synthesis of sodium acrylate from ethylene and CO2 in the presence of alcoholate bases has been improved significantly. We used amide solvents such as N-cyclohexylpyrrolidone or N,N-dibutylformamide to achieve turnover numbers
- Manzini, Simone,Cadu, Alban,Schmidt, Anna-Corina,Huguet, Núria,Trapp, Oliver,Paciello, Rocco,Schaub, Thomas
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p. 2269 - 2274
(2017/06/27)
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- PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT
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A catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt from an alkene, carbon dioxide and an alkoxide having a secondary or tertiary carbon atom directly bound to a [O-] group is described. The alcohol byproduct is distilled off after an intermediate phase separation. This provides pure α,β-ethylenically unsaturated carboxylic acid salt at minimum effort.
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Page/Page column 34
(2016/12/01)
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- Acrylate and acrylic acid recovery method of manufacturing
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PROBLEM TO BE SOLVED: To provide a method for producing acrylate and a method for recovering acrylic acid, requiring no extraction step for unreacted acrylic acid with an organic solvent, making the acrylic acid concentration in the recovery solution high, excellent in recovery efficiency of unreacted acrylic acid and little in impurity amount in the recovery solution. SOLUTION: The method for producing acrylate includes a first step in which acrylic acid and an alcohol are subjected to esterification reaction in the presence of an acid catalyst; a second step in which the reaction solution in the first step is neutralized with an aqueous alkali solution and then separated into an organic phase and an aqueous phase, and the organic phase is fractionated to recover acrylate; a third step in which the aqueous phase of the second step is preparatively collected, and the aqueous phase is added with a sulfuric acid aqueous solution and cooled while the pH is made to be ≤4.0 or cooled after the pH is made to be ≤4.0 to separate it into a solid phase and an aqueous phase [aqueous phase (3)] containing a large amount of acrylic acid (salt), and the content of the acrylic acid (salt) in the aqueous phase (3) is made to be ≥10 wt.% in terns of acrylic acid; and a fourth step in which the solid phase of the third step is separated and then the aqueous phase containing acrylic acid (salt) is recovered. COPYRIGHT: (C)2013,JPOandINPIT
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Paragraph 0060-0063; 0065-0067
(2016/12/22)
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- Acrylate formation from CO2 and ethylene: catalysis with palladium and mechanistic insight
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We report the first catalyst based on palladium for the reaction of CO2, alkene and a base to form sodium acrylate and derivatives. A mechanism similar to a previously reported Ni(0)-catalyst is proposed based on stoichiometric in situ NMR experiments, isolated intermediates and a parent palladalactone. Our palladium catalyst was applied to the coupling of CO2 with conjugated alkenes.
- Stieber, S. Chantal E.,Huguet, Núria,Kageyama, Takeharu,Jevtovikj, Ivana,Ariyananda, Piyal,Gordillo, Alvaro,Schunk, Stephan A.,Rominger, Frank,Hofmann, Peter,Limbach, Michael
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supporting information
p. 10907 - 10909
(2015/06/30)
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- PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT USING AN ARYLOXIDE
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Catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, wherein an alkene and carbon dioxide are reacted in the presence of a carboxylation catalyst and in the presence of a specific aryloxide to obtain the α,β-ethylenically unsaturated carboxylic acid salt, the carboxylation catalyst being a transition metal complex. The process allows for efficient preparation of α,β-ethylenically unsaturated carboxylic acid derivatives from CO2 and an alkene.
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Page/Page column 34; 35; 39
(2016/01/08)
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- PREPARING AN UNSATURATED CARBOXYLIC ACID SALT FROM AN ALKENE AND CARBON DIOXIDE USING A COVALENTLY IMMOBILIZED TRANSITION METAL COMPLEX
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Process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising, reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and releasing the α,β-ethylenically unsaturated carboxylic acid salt with a base, wherein the carboxylation catalyst comprises a transition metal complex that is covalently immobilized on a solid support. The crude reaction product can be processed with little effort to obtain the carboxylic acid derivative at a purity level suitable for further processing into sanitary products.
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Page/Page column 37
(2016/01/29)
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- PROCESS FOR PREPARING AN UNSATURATED CARBOXYLIC ACID SALT
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Catalytic process for preparing an α,β-ethylenically unsaturated carboxylic acid salt, comprising reacting an alkene and carbon dioxide in the presence of a carboxylation catalyst and releasing the α,β-ethylenically unsaturated carboxylic acid salt with a base, the carboxylation catalyst being a transition metal complex, which comprises a structurally constrained bidentate P,X ligand, wherein X is selected from the group consisting of P, N, O, and carbene, the P and X atom are separated by 2 to 4 bridging atoms, and wherein the bridging atoms are part of at least one 5- to 7-membered cyclic substructure. A further catalytic processes for preparing α,β-ethylenically unsaturated carboxylic acid derivatives from CO2 and an alkene is provided.
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Page/Page column 30
(2016/04/26)
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- Nickel-catalyzed direct carboxylation of olefins with CO2: One-pot synthesis of α,β-unsaturated carboxylic acid salts
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The nickel-catalyzed direct carboxylation of alkenes with the cheap and abundantly available C1 building block carbon dioxide (CO2) in the presence of a base has been achieved. The one-pot reaction allows for the direct and selective synthesis of a wide range of a,b-unsaturated carboxylates (TON>100, TOF up to 6 h-1, TON= turnover number, TOF=turnover frequency). Thus, it is possible, in one step, to synthesize sodium acrylate from ethylene, CO2, and a sodium salt. Acrylates are industrially important products, the synthesis of which has hitherto required multiple steps.
- Huguet, Nfflria,Jevtovikj, Ivana,Gordillo, Alvaro,Lejkowski, Michael L.,Lindner, Ronald,Bru, Miriam,Khalimon, Andrey Y.,Rominger, Frank,Schunk, Stephan A.,Hofmann, Peter,Limbach, Michael
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supporting information
p. 16858 - 16862
(2015/01/09)
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- METHODS FOR THE SYNTHESIS OF DEUTERATED ACRYLATE SALTS
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A method for synthesizing a deuterated acrylate of the Formula (1), the method comprising: (i) deuterating a propiolate compound of Formula (2) to a methyne-deuterated propiolate compound of Formula (3) in the presence of a base and D2O: and (ii) reductively deuterating the methyne-deuterated propiolate compound of Formula (3) in a reaction solvent in the presence of deuterium gas and a palladium-containing catalyst to afford the deuterated acrylate of the Formula (1). The resulting deuterated acrylate compounds, derivatives thereof, and polymers derived therefrom are also described.
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Paragraph 0057-0064
(2013/04/10)
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- PREPARATION OF α,β-ETHYLENICALLY UNSATURATED CARBOXYLIC SALTS BY CATALYTIC CARBOXYLATION OF ALKENES
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In a process for preparing an alkalimetalor alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a)a transition metal-alkene complex is reacted with CO2 to give a metallalactone, b)the metallalactone is reacted with a base to give an adduct of the alkalimetal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c)the adduct is reacted with an alkene to release the alkalimetalor alkaline earth metalsalt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The baseis selected from alkalimetal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases.The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.
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Page/Page column 22-23
(2013/07/19)
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- Preparation of a,B-Ethylenically Unsaturated Carboxylic Salts By Catalytic Carboxylation Of Alkenes
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In a process for preparing an alkali metal or alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a) a transition metal-alkene complex is reacted with CO2 to give a metallalactone, b) the metallalactone is reacted with a base to give an adduct of the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c) the adduct is reacted with an alkene to release the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The base is selected from alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases. The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.
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Paragraph 0142; 0143
(2013/07/19)
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- Lewis acid induced β-elimination from a nickelalactone: Efforts toward acrylate production from CO2 and ethylene
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The Lewis acid tris(pentafluorophenyl)borane was found to rapidly promote ring-opening β-hydride elimination in a 1,1′-bis(diphenylphosphino) ferrocene (dppf) nickelalactone complex under ambient conditions. The thermodynamic product of nickelalactone ring-opening was characterized as (dppf)Ni(CH(CH3)CO2BArf3), the result of β-hydride elimination and subsequent 2,1-insertion from a transient nickel(II) acrylate hydride intermediate. Treatment of (dppf)Ni(CH(CH3)CO2BArf3) with a nitrogen-containing base afforded a diphosphine nickel(0) η2- acryl borate adduct. Formation of the diphosphine nickel(0) η2- acryl borate adduct completes a net conversion of nickelalactone to acrylate species, a significant obstacle to catalytic acrylate production from CO 2 and ethylene. Displacement of the η2-acrylate fragment from the nickel center was accomplished by addition of ethylene to yield a free acrylate salt and (dppf)Ni(CH2CH2).
- Jin, Dong,Schmeier, Timothy J.,Williard, Paul G.,Hazari, Nilay,Bernskoetter, Wesley H.
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p. 2152 - 2159
(2013/05/22)
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- The first catalytic synthesis of an acrylate from CO2 and an alkene-A rational approach
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For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C1 building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we
- Lejkowski, Michael L.,Lindner, Ronald,Kageyama, Takeharu,Bodizs, Gabriella E.,Plessow, Philipp N.,Mueller, Imke B.,Schaefer, Ansgar,Rominger, Frank,Hofmann, Peter,Futter, Cornelia,Schunk, Stephan A.,Limbach, Michael
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supporting information
p. 14017 - 14025
(2013/01/15)
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- CURABLE RESIN COMPOSITION FOR COVERING A FINGERNAIL OR ARTIFICIAL FINGERNAIL
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The present invention provides a curable resin composition for coating natural or artificial nails, which in particular exhibits an excellent appearance after coating, high water and scratch resistances, and low levels of odor, damage to nails, and dermal irritancy, resulting in a high level of safety to human bodies and superior storage stability. The curable resin composition for coating a natural or artificial nail of the present invention comprises (A) an aqueous emulsion of a polymer having functional groups polymerizable by exposure to active energy radiation, (B) polyethylene glycol, and (C) a photo radical initiator containing no nitrogen atom in its molecule.
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- A method for preparing sodium acrylate-d3, a useful and stable precursor for deuterated acrylic monomers
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A convenient and economical method for converting propiolic acid to sodium acrylate-d3 is described. Successive D/H exchange of the alkyne proton of sodium propiolate (prepared from propiolic acid) using D2O affords sodium propiolate-d having up to 99 at.% D. Sodium propiolate-d can be partially reduced to sodium acrylate-d3 with 90% conversion and 89% yield using D2 and the Lindlar catalyst, with control of reaction parameters to maximize conversion while minimizing over-reduction. Copyright 2011 John Wiley & Sons, Ltd. A three-step synthetic route for preparing sodium acrylate-d3 in high yield and high isotopic purity from propiolic acid is described. Copyright
- Yang, Jun,Hong, Kunlun,Bonnesen, Peter V.
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experimental part
p. 743 - 748
(2012/01/13)
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- Neutralization Process
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The invention relates to a continuous neutralization process in which at least one ethylenically unsaturated carboxylic acid is neutralized at least partly with a base and the temperature of the neutralized solution is less than 70° C., and also to an apparatus for carrying out the process.
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Page/Page column 6-7
(2008/12/07)
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- Method and apparatus for conversion of beta-hydroxy carbonyl compounds
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A process and apparatus are disclosed for conversion of β-hydroxy carbonyl compounds forming useful conversion products including, e.g., acrylic acid [CAS No. 79-10-7], acrylates, and acrylamide [CAS No. 79-06-01]. Conversion products find use, e.g., as feedstock and/or end-use chemicals.
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Page/Page column 10-11
(2010/11/28)
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- Method for conversion of beta-hydroxy carbonyl compounds
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A process is disclosed for conversion of ammonium salts of β-hydroxy carbonyl compounds forming useful conversion products including, e.g., α, β-unsaturated carbonyl compounds and/or ammonium salts of α, β-unsaturated carbonyl compounds recovered at a high molar yield. Conversion products find use, e.g., as feedstock and/or end-use chemicals.
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Page/Page column 10-11
(2008/06/13)
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- Method for conversion of beta-hydroxy carbonyl compounds
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A process is disclosed for conversion of salts of β-hydroxy carbonyl compounds forming useful conversion products including, e.g., α,β-unsaturated carbonyl compounds and/or salts of α,β-unsaturated carbonyl compounds. Conversion products find use, e.g., as feedstock and/or end-use chemicals.
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Page/Page column 10
(2008/06/13)
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- Polymerized hydrogel adhesives with low levels of monomer units in salt form
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The present invention relates to hydrogel adhesives for attachment to mammalian skin which exhibit particularly good attachment in excess moisture conditions, through the solution of the rheology conditions and level of monomers in salt form. According to a specific embodiment of the present invention, hydrogel compositions are provided, which provide particularly good peel strength and cohesiveness properties; through the selection of monomer unit type of degrees of neutralization. The present invention also encompasses personal care products containing the active adhesives, such as disposable waste management articles, disposable absorbent articles, and various functional articles for attachment to the human body.
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- METHODS OF MANUFACTURING DERIVATIVES OF β-HYDROXYCARBOXYLIC ACIDS
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Preparation of derivatives of β-hydroxycarboxylic acid, including β-hydroxycarboxylic acid esters, α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acid, and alkoxy derivatives.
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Page/Page column 11
(2008/06/13)
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- Fluorination process using hydrogen fluoride-containing fluorinating agents
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Fluorination processes using hydrogen fluoride-containing fluorinating agents that are safely and easily handled, transported, and stored and that also exhibit good reactivity are provided. More particularly, the invention provides processes for producing fluorinated products using fluorinating agents comprising hydrogen fluoride and a carrier that may be an acid salt or a water-soluble polymer.
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- Hydrolysis of 4-acrylamido-4-methyltetrahydrothiophene-3-sulfonic acid 1,1-dioxide
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The hydrolytic stability of a new acrylic monomer, 4-acrylamido-4-methyltetrahydrothiophene-3-sulfonic acid 1,1-dioxide, its homopolymer, and the acetamide and methacrylamide analogs was studied in acidic, neutral, and alkaline media.
- Kazakov,Shirshin,Kazantsev,Danov
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p. 1611 - 1614
(2007/10/03)
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- Acrylate ester
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The present invention concerns a method for the production of olefin anhydrides, such as acrylic anhydride and methacrylic anhydride, via reactions between an aromatic acid chloride, such as benzoyl chloride, and carboxylate ions of the olefin acid corresponding to the anhydride to be produced. The method of the invention may be conducted without the use of a solvent, catalyst, polymerization inhibitor, or an external source of heat. Moreover the acrylic anhydrides of the invention can be used to produce high yields of acrylate esters by means of room-temperature reactions, without mineral acid catalysis.
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- Process for the preparation of bromo-substituted aromatic esters of α,β-unsaturated acids
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A process for the preparation of bromo-substituted aromatic esters of α, β-unsaturated acids of the formula STR1 wherein n is 1 or 2, x=6'n, and R and R' are hydrogen or alkyl; comprises reacting a salt of α,β-unsaturated acid and an alkali with a bromo-substituted benzyl halide in an inert substantially water-immiscible solvent and in the presence of a phase-transfer catalyst.
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- Disubstituted aliphatic carboxylamidoamines as well as detergents and toiletry compositions containing same
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Disubstituted aliphatic carboxylamidoamines of the general formula: STR1 wherein R stands for an aliphatic hydrocarbyl group with 7-17 carbon atoms and M for a hydrogen atom or an alkali metal atom. Detergents and toiletry compositions incorporated with the disubstituted aliphatic carboxylamidoamines are extremely low in irritating property to skin, eyes and mucous membranes.
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