Glycidyl Acetate Research Articles

A facile method to synthesis of a highly acrylated epoxidized soybean oil with low viscosity: Combined experimental and computational approach

This investigation deals with the introduction of an efficient technique to acrylate almost all of the epoxide groups on epoxidized soybean oil (ESO) and synthesize a highly acrylated ESO (AESO) by using viscosity control agents (VCAs). The effect of chemical structure, content, and addition step of VCAs (i.e. glycidyl neodecanoate, glycidyl hexanoate, and glycidyl acetate) on the reaction rate and viscosity was examined. Spectroscopy and analytical analyses as well as viscosity monitoring were employed to assess the acrylation reaction comprehensively. The intermolecular interactions were visualized by molecular dynamics simulation and quantified via the calculation of cohesion energy density to justify the viscosity changes during the reactions. Results demonstrated that the rate of ring-opening reaction is impaired by viscosity severely. Subsequently, the know-how for preparing the AESO with an acrylation degree of 3.5 via optimum reaction conditions was presented. Accordingly, this attempt indicated that the AESO diluted by acrylated glycidyl neodecanoate can be considered a promising oligomer along with other prominent diluents such as trimethylolpropane triacrylate and hexanediol diacrylate to prepare industrial light/UV-curable coatings with perfect performance (gel fraction: 97%, MEK double rub resistance: 75, Tg: 47 °C, hardness: 123, cross-cut adhesion: 4B, gloss: 97.5%, and water contact angle: 89°).

ChemInform Abstract: Concomitant Epoxide Deoxygenation and Deacetylation of Glycidyl Acetates Induced by Telluride Ion.

Treatment of glycidyl acetates with telluride ion (Te 2- ) produced by reduction of elemental Te with LiEt 3 BH yields allylic alcohols by loss of the epoxide oxygen atom and the acetyl group from the ester. If the glycidyl acetate is disubstituted at C-3, a rearrangement to an isomeric allylic alcohol competes with the deoxygenation-deacetylation. Triethylborane, a byproduct in the reduction of Te, is believed to play an important role as a Lewis acid since when it is absent or removed by addition of fluoride ion the reaction is extremely slow

Selective epoxidation of allyl acetate with tert-butyl hydroperoxide over MoO 3/MgO

Highly selective epoxidation of allyl acetate was carried out over MoO 3/MgO using tert-butyl hydroperoxide as an oxidizing agent. The catalytically active species was identified as monolayer MgMoO 4 on MgO. MgO with large pores is suitable for selective epoxide formation. The highest yield of glycidyl acetate was obtained over 7 wt.% MoO 3/MgO, in which MgMoO 4 species were highly dispersed on the surface of MgO. Trialkyl borates were good promoters for selective epoxide formation. Among them, triisopropyl borate afforded the highest yield of 92%. 1H and 11B NMR measurements of a homogeneous MoO 2(acac) 2-B(OBu n ) 3-( t-C 4H 9OOH) system showed that alkyl groups of the borate exchange with t-butyl hydroperoxyl group, and that the boron atom interacts with the oxygen of Mo O, promoting reactivity of an oxygen atom in the hydroperoxyl group to attack the double bond of allyl acetate.

Epoxidation of allyl acetate with tert-butyl hydroperoxide over MoO 3/α-Al 2O 3 promoted by pyridine derivatives

Epoxidation of allyl acetate was carried out over MoO 3/α-Al 2O 3 using tert-butyl hydroperoxide (TBHP) as an oxidizing reagent. Only a small amount of glycidyl acetate was formed. The low yield was due to the cleavage of an epoxy-ring of glycidyl acetate with the acid sites of MoO 3/α-Al 2O 3. The acid sites were neutralized with amines to keep the glycidyl acetate intact during the reaction. Pyridine derivatives greatly improved epoxide selectivity, but addition of aliphatic amines and 2,2′-bipyridine only resulted in retardation of the reaction. The volcano-type plot of Hammett’s p-substituent constant versus epoxide selectivity indicated that pyridine derivative also exerts a ligand effect, and non-substituted pyridine was found to the most suitable additive. The optimum amount of loading of MoO 3 was 2 wt.%; at this value, MoO 3 was highly dispersed on α-Al 2O 3. The optimum molar ratio of pyridine to MoO 3 for epoxide production was 2/3.

Reactivity of Some Carboxylic Acids in Reactions with Some Epoxides in the Presence Chromium (III) Ethanoate

Reactivities have been compared of acetic, acrylic, and methacrylic acid in reactions with epichlorohydrin, phenylglycidyl ether, glycidyl acetate, and glycidyl methacrylate carried in the presence of chromium (III) ethanoate. The acid reactivities changed differently with respect to the oxirane series. The effect of solvents on the reactions of acids with epichlorohydrin has also been observed.

Isomerization polymerization and copolymerization of glycidyl alkanoates catalyzed by methylaluminum bis(2,6-di-t-butyl-4-methylphenoxide)

The isomerization polymerizations of glycidyl propionate (1b), octanoate (1c), and stearate (1d) with methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (3) were investigated. The polymerizations selectively gave poly(2-alkyl-1,3-dioxolane-4,2-diyloxymethylene)s (2), although the polymer yield as well as the polymer molecular weight significantly decreased as the acyl chain of 1 was lengthened. These polymers readily hydrolyzed to glycerin and the corresponding fatty acids under mild conditions. The copolymerizations of glycidyl acetate (1a) with these monomers were also examined. In any combination, the composition of the obtained copolymer was essentially identical with the feed ratio, while both copolymer yield and molecular weight decreased as the feed of 1a was decreased. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 435–444, 1999 (See graphics.)

Novel Isomerization Polymerization of Glycidyl Acetate To Produce a Poly(ortho ester)

A new mode of polymerization of glycidyl acetate (1a) to yield a poly(ortho ester), i.e., poly[(2-methyl-1,3-dioxolane-4,2-diyl)oxymethylene] (3a), was explored. This new polymerization exclusively proceeded when a bulky Lewis acid, methylaluminium bis(2,6-di-tert-butyl-4-methylphenoxide) (2a), was employed as the catalyst. The polymerization of 1a with 4 mol % of 2a proceeded smoothly in toluene at 0 °C and gave 3a in 82% after 1 h. The time-trace of the polymerization system revealed that this polymerization was completed within 3 min under these conditions. The polymerization mechanism is tentatively assumed as polyaddition of zwitterionic species produced from 1a with the assistance of 2a. The polymerization of glycidyl methacrylate (1b) with 2a gave poly(ortho ester) 3b in a similar manner.

The thermal degradation of copolymers of glycidyl methacrylate and vinylacetate

The thermal degradation of copolymers of glycidyl methacrylate (GMA) and vinyl acetate (VAc) was studied by thermal volatilisation analysis (TVA), thermogravimetry (TG), differential thermal analysis (DTA), and pyrolysis mass spectrometry. The apparent activation energies for the decomposition of the copolymers were calculated from the results of TG experiments. The condensable volatile products from the TVA experiments have been identified after separation by subambient thermal volatilisation analysis (SATVA). The cold ring fraction (CRF) was examined by FTIR spectroscopy, and the structural changes in the residue in the course of degradation were also examined. Non-condensable products formed during TVA degradation were identified by mass spectrometry. These copolymers display a new reaction not found in either of the homopolymers, namely adjacent unit lactonisation. Particular features which distinguish the behaviour of the copolymers from the homopolymers are: (a) the low yield of GMA, and (b) the appearance of glycidyl acetate as one of the major products. A mechanism of thermal degradation has been suggested.

On the Ionic Species Formed in Reactions of Sulfur Dioxide with Cyclic Ethers and Propylene Sulfide

The reactions of SO2 with various oxiranes, propylene sulfide, and oxetane have been studied. It was found that SO2 activates these monomers toward ring opening polymerization. The spontaneous reactions lead to the formation of cationic active centers, on which the heterocyclic monomer homopropagation and various cyclization processes mainly proceed. Anionic alternating copolymerization of SO2 with ethylene oxide or propylene oxide was observed after the spontaneous termination of cationic active species. Zwitterions with active anionic sites are formed in the presence of pyridine. They can initiate the alternating copolymerization of SO2 and oxiranes. The relative reactivity of the oxiranes in the addition to anionic species increases in the following order: epichlorohydrin < glycidyl acetate < propylene oxide < butyl glycidyl ether < ethylene oxide < 1,2-cyclohexene oxide. Styrene oxide, oxetane, and propylene sulfide undergo spontaneous reactions also in the presence of pyridine. In systems with the f...

Kinetics of addition of acetic acid to epichlorohydrin in the presence of alkali metal acetates

AbstractThe kinetics of the reaction between acetic acid and epichlorohydrin in the presence of lithium, sodium and potassium acetates have been studied. The composition of the reaction mixture was followed chromatographically. Beside the two isomeric products of addition of epichlorohydrin to acetic acid, the presence was found of glycidyl acetate, glycerine dichlorohydrin and other products of parallel and subsequent reactions between the substrates and chlorohydroxyesters. A mechanism of the reaction, which takes into account the formation of the identified compounds has been proposed and a set of appropriate differential and balance equations developed. The rate constants for individual reactions as well as the catalysts used have been determined.

Improvement of lipase-catalyzed kinetic resolution by tandem transesterification

Glycidyl acetate may be prepared enantioselectively from glycidyl butyrate by sequential enzymatic resolution. First, porcine pancreas lipase selectively forms ( R)-glycidol by transesterification in dehydrated butanone. Then the lipase transesterifies ( R)-glycidol selectively to glycidyl acetate. A model incorporating ping-pong bi-bi kinetics for this tandem reaction was worked out. For both reaction steps the enantiomeric ratios were 7. Other model parameters were also determined. The experimental results were adequately described by the model. The maximum enantiomeric excess of glycidyl acetate was raised from 65 to 89% by carrying out a tandem reaction instead of a single-resolution reaction. However, the model predicts that the amount of enantiopure product that may be obtained in a tandem reaction is limited as a result of equilibrium restrictions.

Polymères porteurs de dérivés du glycérol, 10. Fixation de l'acide naphtyl‐1 acétique sur le poly(acide méthacrylique)

Glycidyl (2,3-epoxypropyl) esters are convenient reagents for the fixation of carboxylic acid moieties on polymeric support of the polyacid type. This way of synthesis was applied to 1-naphthylacetic acid on poly(methacrylic acid). Esterification of 1-naphthylacetyl chloride by glycidol (2,3-epoxy-1-propanol) and addition of 1-naphthylacetic acid on epichlorohydrin (1-chloro-2,3-epoxypropane) with subsequent reformation of the oxirane ring have been used for the synthesis of the glycidyl ester but the reaction of the potassium salt of the acid with epichlorohydrin leads to a better yield. Addition of 1-naphthylacetic acid on glycidyl acetate was studied in N,N-dimethylformamide (DMF) and acetonitrile. The best results were obtained in DMF. The reaction is of first order with respect of epoxide, but 2nd order applies when the solvent is acetonitrile. The same reaction conditions as for glycidyl acetate were used for the chemical modification of poly(methacrylic acid) with glycidyl 1-naphthylacetate except that methanol was used as the solvent.

Concomitant Epoxide Deoxygenation and Deacetylation of Glycidyl Acetates Induced by Telluride Ion

Treatment of glycidyl acetates with telluride ion (Te 2- ) produced by reduction of elemental Te with LiEt 3 BH yields allylic alcohols by loss of the epoxide oxygen atom and the acetyl group from the ester. If the glycidyl acetate is disubstituted at C-3, a rearrangement to an isomeric allylic alcohol competes with the deoxygenation-deacetylation. Triethylborane, a byproduct in the reduction of Te, is believed to play an important role as a Lewis acid since when it is absent or removed by addition of fluoride ion the reaction is extremely slow

Kinetic aspects of the reaction of succinoylated dextran with glycidyl acetate

This work deals with the reaction of succinoylated dextran with glycidyl acetate (a model compound of glycidyl bioactive derivative) using benzyltriethylammonium chloride as catalyst. The reaction shows second order kinetics and depends on the glycidyl acetate and catalyst concentrations, showing no dependence on the acid groups' concentration. On the basis of these findings a probable mechanism of the reaction is suggested.

Fermentation of glucose in glycerol-stereochemistry of the proton transfer mediated by phosphoglucoisomerase:a deuterium NMR proof.

An unambiguous deuterium NMR evidence of the stereochemistry of the proton transfer mediated by phosphoglucoisomerase is given. The methodology used involves the fermentation of a slightly enriched [1- 2H]-glucose into glycerol, the latter being transformed further on into glycidyl acetate which is a more suitable structure for 2H NMR studies.

Catalytic Additions of Oxiranes with Carbon Dioxide through Free Anions Activated by a Crown Ether

Free anionic additions of oxirane and its alkyl, aryl and halomethyl derivatives with carbon dioxide catalyzed by potassiim carboxylates or carbonates have been achieved by the addition of a crown ether, resulting in the formation of five-membered cyclic carbonates as the main products. In the absence of carbon dioxide, the potassium salts initiated the polymerization of oxirane and alkyl- and aryloxiranes to afford polyethers having the carbonyl end group at one of the chain ends. Halomethyloxiranes were not polymerized under the same conditions and reacted stoichiometrically with potassium acetate to give glycidyl acetate in high yields. The reactions between halomethyloxiranes and potassium ethyl carbonate gave a variety of products including linear and cyclic carbonates. A reaction scheme is proposed to interpret all the results consistently.

An electron spin resonance study of 3-oxypropenoyl radicals derived from glycidols

Glycidols with blocked OH groups (A; M = alkyl or trialkylsilyl) react with t-butoxyl radicals to show the e.s.r. spectra of the corresponding 3-oxypropenoyl radicals (D), and 24 examples of these acyl radicals are reported. The [graphic ommitted] reaction is thought to proceed through the formation of the allyloxyl radicals (B), which, in part, are converted into the aldehyde (C) which is very reactive towards loss of hydrogen to give the acyl radical (D). Glycidyl pivalate (A; M = COCMe3) reacts cleanly in this way, but glycidyl acetate (E; R = Me) also undergoes intramolecular 1,5-transfer of the acyl group to show the spectrum of the enoxyl radical (F). Glycidyl propionate and butyrate do not undergo this acyl transfer, but show the spectra of the radicals OĊCHCHOCOCH2R′ and [graphic omitted]HCH2OCOĊHR′(R′= Me or Et). [graphic ommitted]

Vinyl polymerization. 81. The effect of glycidyl methacrylate on the polymerization of tetrahydrofuran catalyzed by boron trifluoride‐diethyl ether complex

AbstractThe effect of glycidyl methacrylate (GMA) on the polymerization of tetrahydrofuran (THF) catalyzed by boron trifluoride‐diethyl ether complex at 0°C. has been investigated. Glycidyl acetate (GA) was used as a reference compound for GMA. GMA and GA acted as cocatalysts and fibrous, highly crystalline and high molecular weight poly‐THF was obtained. GMA and GA could also serve as a comonomer; the resulting oily or waxy copolymers of GMA contained unsaturation from GMA units. The copolymers with GMA were cured by heating and grafted to styrene and methyl methacrylate in the presence of radical initiators.