75825-77-3

Upstream product

• 56-81-5 glycerol 
• 78-93-3 butanone 
• 100-79-8 (R,S)-2,2-dimethyl-1,3-dioxolane-4-methanol 

Relevant academic research and scientific papers

Solvent-free heteropolyacid-catalyzed glycerol ketalization at room temperature

Currently, glycerol has been produced in large amounts as a biodiesel co-product. Therefore, developing processes to convert it into more valuable chemicals has attracted significant attention. Glycerol ketals are compounds useful as synthesis intermediates, fragrance ingredients, and mainly bioadditives for diesel and gasoline, and have been produced from reactions catalyzed by mineral acids. In this work, we assessed the activity of H3PW12O40 heteropolyacid on glycerol ketalization with different ketones at room temperature and in the absence of an auxiliary solvent. The effects of the principal reaction parameters such as the reactant stoichiometry, catalyst concentration, reaction temperature, and type of carbonylic reactant were investigated. H3PW12O40 heteropolyacid was much more active than other Br?nsted acid catalysts evaluated (i.e. H2SO4, p-toluenesulfonic acid, H3PMo12O40 or H4SiW12O40) and exhibited high selectivity toward five-membered (1,3-dioxolane) cyclic ketals. Although homogeneous, the heteropolyacid catalyst could be recovered and reused without a loss of activity.

Synthesis of a H-Sulfo-POSS catalyst and application in the acetalization of glycerol with 2-butanone to yield a biofuel additive

Nanosized polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular weight enlarged structures for different purposes owing to their ease of synthesis and modification. In this work, the commercially available compound octaphenyl-POSS has been modified with chlorosulfonic acid to obtain multifunctional acidic materials (H-Sulfo-POSS) with different degrees of functionality in the structure. The synthesized materials have been characterized by ion exchange capacity, degree of sulfonation,1H-NMR, ATR-IR spectroscopy and SEM. These H-Sulfo-POSS nanocomposites were then applied to the acetalization of glycerol with 2-butanone to yield the corresponding ketal, which is a product of interest as an oxygenate fuel additive. The catalytic activity in dynamic experiments of the H-Sulfo-POSS (2601 h?1) material with the highest degree of sulfonation was even higher than that shown by the molecular catalystpara-toluene sulfonic acid (PTSA) (2256 h?1) and better than Amberlyst 36 (213 h?1); however, upon recycling by centrifugation of the catalyst, the activity of this material was not very stable. On the other hand, the material with the lowest degree of sulfonation showed not only higher activity than Amberlyst 36, but also very stable activity after reutilization throughout 10 runs.

Solvent-free ketalization of polyols over germanosilicate zeolites: The role of the nature and strength of acid sites

Isomorphic substitution of silicon for germanium affords germanosilicate zeolites with weak acid centers capable of catalyzing key reactions such as Baeyer-Villiger oxidation of ketones and etherification of levulinic acid. Herein, we show for the first time that UTL (Si/Ge = 4.2) and IWW (Si/Ge = 7.2) germanosilicate zeolites are active and selective catalysts of polyol (e.g., ethylene glycol, glycerol and 1,4 butanediol) ketalization to dioxolanes. Large-pore IWW outperformed the extra-large-pore UTL zeolite in the ketalization of polyols, thus indicating diffusion limitations in bulky platelet-like UTL crystals. FTIR spectroscopy of adsorbed pyridine revealed the Lewis acidity of the UTL zeolite, whereas the more active IWW catalyst was characterized by water-induced Br?nsted acidity. Increasing the activation temperature (200-450 °C) reduced the concentration of Br?nsted acid centers in the IWW germanosilicate (i.e., 0.16; 0.07 and 0.05 mmol g-1 for Tact = 200, 300 and 450 °C, respectively) but increased the number of Lewis acid sites in both zeolites. Under optimized reaction conditions (e.g., acetone/glycerol = 25, Tact = 300 °C), almost total transformation of glycerol into solketal was achieved within 3 h of reaction time over the IWW zeolite at room temperature (>99% yield of the target product). The results from the present study clearly show that weak acid centers of germanosilicate zeolites can serve as active sites in ketalization reactions.

Method for preparing ketal glycerine and/or acetal glycerine by catalyzing glycerine

The invention relates to a method for preparing ketal glycerine and/or acetal glycerine by catalyzing glycerine. The method comprises the following steps: contacting glycerine and a reaction raw material with a catalyst in a reactor, and reacting to obtain a product containing ketal glycerine and/or acetal glycerine, wherein the reaction raw materials contains aldehyde and/or ketone, the molar ratio of glycerine to aldehyde and/or ketone is 1:(1-10), the reaction temperature is 30-180 DEG C, the reaction time is 1-10 hours, the catalyst contains a tin-silicon molecular sieve, and the weight ratio of glycerine to the tin-silicon molecular sieve based on dry basis weight is (1-40):1, the tin-silicon molecular sieve contains a silicon element, a tin element and an oxygen element, a cavity orcavity structure is formed in all or part of crystal grains, the total specific surface area is larger than or equal to 300 m/g, and the proportion of the external specific surface area to the total specific surface area is larger than or equal to 10%. The method provided by the invention has high aldehyde/ketone conversion rate and high acetal/ketal glycerine selectivity.

METHOD FOR PRODUCING GLYCERIC ACID ESTER

The present invention is to provide a method of producing a glyceric acid ester which is easy for production and high in yield, and in which a pyridine to be used for the reaction is easily reused. Provided is a method of producing a compound represented by the following formula (II), including a step of oxidatively esterifying Compound A represented by the following formula (I) with Compound B selected from an organic nitroxyl radical, an N-hydroxy form thereof, and a salt containing an oxo ammonium cation of them, and an oxidizing agent in the presence of a pyridine having an alkyl substituent, wherein the use amount of Compound B is 0.0001 or more and 0.1 or less in terms of a molar ratio relative to Compound A: wherein, in the formulae (I) and (II), R1 and R2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R1 and R2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

COALESCING AGENT DERIVED FROM DIOXOLANE DERIVATIVES

The present invention relates to a coalescing agent as represented in structure (I); wherein; n is integer from 1 to 8; R1 and R2 independently represent group selected from hydrogen atom, alkyl, alkenyl, alkynyl, phenyl, benzyl groups, or optionally cyclic hydrocarbon containing heteroatom; and Y represents group selected from alkyl, alkenyl, alkynyl, phenyl, benzyl groups, or cyclic hydrocarbon containing heteroatom. The said coalescing agent can be used in coating application with efficacy to provide smooth consistent film with chemical and scratch resistant and has no pungent odour, wherein the preparation method of this compound is simplify and employs less harmful chemicals.

Acetalization of glycerol with ketones and aldehydes catalyzed by high silica Hβ zeolite

In this work, proton-exchanged *BEA zeolite with a high Si/Al ratio of 75 (Hβ-75), was demonstrated as an effective catalyst for the acetalization of glycerol with carbonyl compounds. This catalyst system was applicable to various substrates and reusable for at least 4 times with slight decrease in activity. The turnover frequency, based on acid site concentration, increased as a function of Hβ Si/Al ratio, indicating the importance of the zeolite hydrophobic surface properties. The origin of the high efficiency exhibited by Hβ-75 is quantitatively discussed based on kinetic studies, hydrophobicity, and acid site concentration.

Towards a rational design of a continuous-flow method for the acetalization of crude glycerol: Scope and limitations of commercial amberlyst 36 and AlF3· 3H2O as model catalysts

The acetalization of six different types of glycerol including pure, wet, and crude-like grade compounds of compositions simulating those of crude glycerols produced by the biodiesel manufacture, was carried out with two model ketones such as acetone and 2-butanone. The reaction was investigated under continuous-flow (CF) conditions through a comparative analysis of an already known acetalization catalyst such as Amberlyst 36 (A36), and aluminum fluoride three hydrate (AlF3· 3H2O, AF) whose use was never previously reported for the synthesis of acetals. At 10 bar and 25 °C, A36 was a highly active catalyst allowing good-to-excellent conversion (85%-97%) and selectivity (99%) when either pure or wet glycerol was used as a reagent. This catalyst however, proved unsuitable for the CF acetalization of crude-like glycerol (CG) since it severely and irreversibly deactivated in a few hours by the presence of low amounts of NaCl (2.5 wt %) which is a typical inorganic impurity of raw glycerol from the biorefinery. Higher temperature and pressure (up to 100 °C and 30 bar) were not successful to improve the outcome. By contrast, at 10 bar and 100 °C, AF catalyzed the acetalization of CG with both acetone and 2-butanone, yielding stable conversion and productivity up to 78% and 5.6 h-1, respectively. A XRD analysis of fresh and used catalysts proved that the active phase was a solid solution (SS) of formula Al2[F1-x(OH)x]6 (H2O)y present as a component of the investigated commercial AF sample. A hypothesis to explain the role of such SS phase was then formulated based on the Br?nsted acidity of OH groups of the solid framework. Overall, the AF catalyst allowed not only a straightforward upgrading of CG to acetals, but also a more cost-efficient protocol avoiding the expensive refining of raw glycerol itself.

New approach to the synthesis of 1,3-dioxolanes

Application of ethanol to the synthesis of 1,3-dioxolanes by the condensation of carbonyl compounds with vicinal diols results in a high yield of the reaction product and considerably reduces the duration of the process. It is assumed that the effect of the ethanol is caused by the adduct formation with carbonyl compounds (hemiacetals) which behave as active intermediates of the condensation. A cyclic ketal of acetone with glycerol obtained with the help of ethanol was used as a basis component in the synthesis of a series of ketals substituting diol or carbonyl components by transketalyzation mechanism proceeding without water liberation.

Highly regioselective preparation of 1,3-Dioxolane-4-methanol derivatives from glycerol using phosphomolybdic acid

Phosphomolybdic acid (PMA) forms a blue-colored complex with glycerol in a 1:10 molar ratio. The glycerolato complex catalyzes conversion of glycerol into 1,3-dioxolane-4-meth-anol derivatives with complete regiospecificity in high yields (>95%) and the catalyst can be recycled up to ten times without loss of activity or regiospecificity. Georg Thieme Verlag Stuttgart.