Reaction Of Phenyl Glycidyl Ether Research Articles

DBU-intercalated γ-titanium phosphate as a latent thermal catalyst in the reaction of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA).

The capabilities and performance of γ-titanium phosphate (γ-TiP) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a latent thermal catalyst were investigated by the copolymerization of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) at different temperatures for a period of one hour. Polymerization was not observed until the reactants were heated to 100 °C. Upon increasing the temperature to 120 °C, the conversion in the presence of γ-TiP·DBU as a catalyst showed 98% conversion in 1 h. The thermal stability of GPE and MHHPA reacted in the presence of γ-TiP·DBU at 40 °C for 144 h resulted in less than 7% conversion of GPE. The conversion of GPE did not show a significant increase at 40 °C.

Thermosetting epoxy resin system: Ring-opening by copolymerization of epoxide with D,L-Lactide

We examined the ring-opening copolymerization of glycidyl phenyl ether (GPE) and d,l-lactide (LAC) to afford poly(GPE-co-LAC) as a model reaction of the LAC-mediated thermal curing of epoxy resins such as 2,2-bis(4-glycidyloxyphenyl)propane (BGP), 2,2-bis(4-glycidyloxyphenyl)methane (BGM), 3,3′,5,5′-tetramethyl-4,4′-diglycidyloxybiphenyl (TDP), N,N-diglycidyl-4-glycidyloxyaniline (DGA), and oligo phenols (NC-3000 and EPPN-502H). The reaction of GPE and LAC proceeded efficiently in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) at 180 °C for 2 h. The monomer reactivities r1 of LAC and r2 of GPE calculated according to the Fineman-Ross method and the Kelen-Tüdӧs method were 0.85 and 1.26, respectively. The relatively small difference between these values suggests that the produced poly(GPE-co-LAC) would be a gradient copolymer, different from a block copolymer or random copolymer. Based on these results, we examined the thermal curing reactions of epoxy resins BGP, BGM, TDP, DGA, NC-3000, and EPPN-502H in bulk under the same conditions. The corresponding cured products were obtained quantitatively. The thermal stability of BGP, BGM, DGA, and EPPN-502H was increased by the addition of a small amount of LAC, suggesting that the cross-linking density of the cured products was increased. This new class of thermal curing system should be applicable to epoxy resins used in various industrial applications.

Acceleration effects of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene with 2‐methylimidazole‐intercalated α‐zirconium phosphate as a latent thermal initiator in the reaction of glycidyl phenyl ether and hexahydro‐4‐methylphthalic anhydride

ABSTRACTThe catalytic effects of 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene (TBD) with 2‐methylimidazole‐intercalated α‐zirconium phosphate (α‐ZrP∙2MIm) in the reaction of glycidyl phenyl ether (GPE) and hexahydro‐4‐methylphthalic anhydride (MHHPA) were investigated. The reaction did not proceed within 1 h at 60 °C. On increasing the temperature to 100 °C, the conversion reached 93% for 1 h. Without the addition of TBD, the conversion was 67% at 100 °C for 1 h. Under storage conditions at 25 °C for 7 days, the conversion of GPE was only 18%. The curing behavior of 2,2‐bis(4‐glycidyloxyphenyl)propane (DGEBA) and MHHPA in the presence of TBD with α‐ZrP∙2MIm was evaluated by differential scanning calorimetry. The addition of TBD with α‐ZrP∙2MIm as a latent thermal initiator, the storage stability was maintained and the reaction proceeded rapidly under heating conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2557–2561

Temperature-Dependent Enhancement Effects for TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-ene) with 2-Methylimidazole-Intercalated α-Zirconium Phosphate as a Latent Thermal Initiator in the Reaction of Glycidyl Phenyl Ether

The catalytic effects of 1,1,3,3-Tetramethylguanidine (TMG), 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) in the reaction with glycidyl phenyl ether (GPE) at 40 °C were investigated. For the reaction, the %conversion of GPE was only 11%, carried out at 40 °C over 14 days in the presence of TBD.Additionally, there was little catalytic activity for the same reaction performed under typical storage conditions at 25 °C. The effect of TBD with 2-methylimidazole-intercalated α-zirconium phosphate (α-ZrP∙2MIm), as a latent thermal initiating system in the reaction with GPE, was then examined. The reaction did not proceed within 1 h at 80 °C. On increasing the temperature to 120 °C, the %conversion reached 75% for reaction at 1 h. Under typical storage conditions (7 days at 25 °C), the %conversion of GPE was only 7%. With addition of TBD to α-ZrP∙2MIm, reagent stability was maintained, and the polymerization reaction proceeded rapidly with the application of heat.

Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether.

The reaction of phenyl glycidyl ether (PGE) with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate to initiate the polyetherification reaction was examined using thermal and spectral analysis techniques. The influence of the nucleophilicity of the anions on the deprotonation of the 1-ethyl-3-methylimidazolium cation determined the reaction pathway. The thermal degradation of the ionic liquid liberated the acetate ion and led, subsequently, to the deprotonation of the acidic proton in the imidazole ring. Thus, polymerisation of PGE occurred via a carbene intermediate. The more nucleophilic thiocyanate anion was not sufficiently basic to deprotonate the 1-ethyl-3-methylimidazolium cation, and thus proceeded through direct reaction with the PGE, unless the temperature was elevated and a competing carbene mechanism ensued.

Release Behavior of Benzimidazole-Intercalated α-Zirconium Phosphate as a Latent Thermal Initiator in the Reaction of Epoxy Resin

The intercalation compound of benzimidazole with α-zirconium phosphate (α-ZrP) was evaluated as a latent thermal initiator in the reaction of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA). No reaction occurred at 60 °C after 1 h. Upon increasing the temperature to 140 °C, the conversion reached 97% after 1 h. The deintercalation ratio of Bim from the intercalation compound of benzimidazole with α-zirconium phosphate (α-ZrP·Bim) was measured in the reaction of the GPE-MHHPA system. The deintercalation ratio increased upon increasing the temperature, reaching 97% at 120 °C after 1 h. The storage stability at 25 °C and 40 °C in the reaction of GPE-MHHPA was tested and was found to be maintained for 14 days at 25 °C. The intercalation compound of α-ZrP·Bim can effectively serve as a latent thermal initiator in the reaction of GPE-MHHPA.

Synthesis, Characterization, and Evaluation of Surface and Thermal Properties and Cytotoxicity of 2‐Hydroxy‐3‐Phenoxypropyl Imidazolium Bola‐Type Gemini Amphiphiles

AbstractA library of imidazolium‐based gemini cationic bola amphiphiles was synthesized using a regioselective ring‐opening reaction of glycidyl phenyl ether with imidazole under solvent‐free conditions. The corresponding hexafluorophosphate (PF6−) and tetrafluoroborate (BF4−) counterion‐containing amphiphiles were also synthesized and characterized using nuclear magnetic resonance (NMR) and mass spectroscopy. The micellar and interfacial parameters like the critical micelle concentration (CMC), surface pressure at the CMC (Пcmc), surface tension at CMC ( γcmc), counterion binding (β), maximum surface excess concentration ( Γmax), minimum area per molecule ( Amin), standard free energy of micellization () and adsorption (), and Kraft temperature were evaluated using surface tension and conductometry methods in aqueous solution as well as in buffer solution. Dynamic light scattering (DLS) was used to determine the size of the micelles formed in the aqueous solution. Cytotoxicity tests were carried out on the C6 glioma cancerous brain cell line using the MTT assay (3‐(4, 5‐dimethylthiazole‐2‐yl)‐2, 5‐diphenyltetrazolium bromide) to evaluate the IC50 value of all the synthesized amphiphiles. Thermal stability of these amphiphiles was also evaluated using a thermal gravimetric analyzer (TGA). Economic way of synthesis, moderate thermal stability, a low value of CMC, and cytotoxicity of these amphiphiles will inspire new research in the field of nanobiotechnology and pharmaceutical industries.

Identification of the reaction mechanism between phenyl methacrylate and epoxy and its application in preparing low-dielectric epoxy thermosets with flexibility

NORYL™ SA9000 resin is a commercialized telechelic PPO oligomer with phenyl methacrylate end groups. However, neat SA9000 thermoset is brittle after thermally curing. To find a method to enhance the toughness of neat SA9000 thermoset, three model reactions are designed. The first one is the 4-dimethylaminopyridine (DMAP)-catalyzed homopolymerization of glycidyl phenyl ether. The second one is the reaction of glycidyl phenyl ether and phenyl acetate in the presence of DMAP. The third one is the reaction of glycidyl phenyl ether and phenyl methacrylate in the presence DMAP. Through 1H NMR analysis, the product is 1,3-diphenoxy-2-acetoxypropane and 1,3-diphenoxy-2-methacryalatepropane, respectively, for model reactions 2 and 3. According to the structure of products, we identify the reaction mechanisms between the phenyl acetate and epoxy, and between the phenyl methacrylate and epoxy. Based on the knowledge, we used two commercialized epoxy resin (DGEBA and HP7200) to copolymerize with SA9000 in the presence of DMAP and tert-butyl cumyl peroxide (TBCP). The toughness of the thermosets are significantly improved, which means the brittle drawback of neat SA9000 thermoset has been solved. Homogeneous, flexible thermosetting films with high glass transition temperatures, low dielectric constants, and extremely low dissipation factors are obtained.

Imidazoles-Intercalated α-Zirconium Phosphate as Latent Thermal Initiators in the Reaction of Glycidyl Phenyl Ether (GPE) and Hexahydro-4-Methylphthalic Anhydride (MHHPA)

The capabilities of imidazoles-intercalated α-zirconium phosphate (α-ZrP·imidazole): imidazol (α-ZrP·Im), 2-methylimidazole (α-ZrP·2MIm), and 2-ethyl-4-methylimidazole (α-ZrP·2E4MIm) as latent thermal initiators were examined by the copolymerization of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) with the imidazoles-intercalated α-zirconium phosphate at varying temperatures for one-hour periods. Polymerization was not observed until the reactants were heated to 100 °C or above. Increasing the temperature, polymerization in the presence of α-ZrP·Im, α-ZrP·2MIm, or α-ZrP·2E4MIm proceeded at 140 °C for 1 h with over 90% conversion. The thermal stabilities of α-ZrP·Im, α-ZrP·2MIm, and α-ZrP·2E4MIm in the reaction at 40 °C for 264 h were tested. With α-ZrP·2MIm, the conversion was less than 15% up to 96 h. In the cases of α-ZrP·Im and α-ZrP·2E4MIm, the conversion reached less than 15% at 264 h. The thermal stabilities of α-ZrP·Im, α-ZrP·2MIm, and α-ZrP·2E4MIm at 40 °C were superior to those of the commercially available thermal latent initiators: HX-3088 and HX-3722.

Alkylamines-intercalated α-zirconium phosphate as latent thermal anionic initiators

The reaction of glycidyl phenyl ether (GPE) with 1-aminoalkanes-intercalated α-zirconium phosphate (α-ZrP·1-aminoalkane): 1-aminoalkanes 1-aminopropane (α-ZrP·Pr), 1-aminobutane (α-ZrP·Bu), 1-aminooctane (α-ZrP·Oct), and 1-aminohexadecane (α-ZrP·Hed) was carried out at varying temperatures for 1 h periods. Reaction progress was not observed until the reactants were heated to 80 °C or above. On increasing the temperature, the conversion factors increased such that, at 140 °C, conversions of 62% (α-ZrP·Pr), 60% (α-ZrP·Bu), 67% (α-ZrP·Oct), and 64% (α-ZrP·Hed) were obtained. The thermal stabilities as latent initiators were tested: GPEs reacted with α-ZrP·Pr, α-ZrP·Bu, and α-ZrP·Oct at 40 °C for 360 h achieved conversions of 83, 55, and 59%, respectively. In contrast, the reaction in the presence of α-ZrP·Hed did not proceed at 40 °C. The order of the thermal stability of GPE in the presence of α-ZrP·1-aminoalkane intercalation compounds was: α-ZrP·Hed > α-ZrP·Bu ≈ α-ZrP·Oct > α-ZrP·Pr. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1854–1861

Study of chemical processes in the modification of epoxide polymers by aluminum oxide

The processes occurring during the modification of epoxy polymers by various polymorphic aluminum oxide modifications (γ-AlO(OH), γ-Al2O3, α-Al2O3) with epoxy groups were studied by the methods of IR Fourier spectroscopy, chemical analysis, and differential scanning calorimetry (DSC) by an example of a model compound (phenyl glycidyl ether). Two types of interactions were revealed: a direct chemical reaction of phenyl glycidyl ether with the surface hydroxy groups of alyminum oxide, and phenyl glycidyl ether homopolymerization. By processing by graphical method the data of chemical analysis on the diminishing in amount of epoxy groups in the course of the polycondensation reaction the value of activation energy 106–110 kJ mol−1 of the process of phenyl glycidyl ether interaction with aluminum γ-oxide was determined.

Reaction of phenyl glycidyl ether with some heterocycles

The respective hydroxypropyl phenyl ethers were obtained by the reaction of 5,5-dimethylhydantoin, morpholine, benzotriazole, benzimidazole, pyrrolidone, and phthalimide with phenyl glycidyl ether. 8-(2-Hydroxy-3-phenoxy) quinoline was synthesized by O-alkylation.

Thermally latent reaction of hemiacetal ester with epoxide catalyzed by recyclable polymeric catalyst consisting of salen-zinc complex and polyurethane main chain

This article describes the synthesis of and catalysis with a polymeric catalyst (Zn/1NHCOO) carrying salen-zinc complex structure in the main chain prepared from polyaddition of zinc/bis(4-hydroxy)salicylidene-1,2-diiminoethane and 4,4′-diphenylmethane diisocyanate. Poly(Zn/1NHCOO) promoted the reaction of glycidyl phenyl ether (2) with 1-propoxyethyl-2-ethylhexanoate (3) only at moderately elevated temperatures. Poly(Zn/1NHCOO) can be recycled by simple filtration from the reaction mixtures, and the recycled polymer is as active as the freshly prepared one. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3673–3681, 2008

Model reaction for thermally latent curing through addition of hemiacetal ester and epoxide by schiff‐base–zinc halide complexes

AbstractSchiff‐base–zinc halide complexes (ZnX2/1) thermal‐latently catalyze the reaction of glycidyl phenyl ether (2) and 1‐propoxyethyl 2‐ethylhexanoate (3) that proceeds at moderately elevated temperatures. The catalysis by the ZnX2/1 complexes proceeds via the thermal dissociation of 3 to produce the corresponding carboxylic acid that nucleophilically attacks 2 predominantly over the thermally dissociated vinyl ether. ZnX2/1 complexes catalyze both the dissociation of 3 to produce the carboxylic acid intermediate and its addition to 2. Although conventional latent catalysts for this reaction exhibit Lewis acidities under ambient conditions that are responsible to the gradual degradation of hemiacetal esters and the polymerization of epoxides, a mixture of 2, 3, and ZnX2/1 can be stored for 3 months at ambient conditions. The stored mixture is as active as the freshly prepared mixture, keeping the excellent activity and latency of ZnX2/1. As well as the model reaction, the thermally latent polyaddition of bisphenol A diglycidyl ether (9) and di‐1‐propoxyethyl adipate (10) is also promoted with ZnCl2/1 at a moderate elevated temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3370–3379, 2007

Thermally latent reaction of hemiacetal ester with epoxide controlled by Schiff-base–zinc chloride complexes with tunable catalytic activity

Schiff-base–zinc chloride complexes (ZnCl 2 /1 R) thermal-latently catalyze the reaction of glycidyl phenyl ether ( 2) and 1-propoxyethyl-2-ethylhexanate ( 3) that proceeds at appropriate temperatures for latent curing. This reaction proceeds via the nucleophilic addition of carboxylic acid generated from the thermal dissociation of 3 to 2, which takes place faster than the reaction without ZnCl 2 /1 R. Catalytic activities of ZnCl 2/ 1 R, depending on the basicities of the α-diimine ligands controllable by the substituents on the aromatic rings, were evaluated by kinetic parameters; namely the reaction rate constants ( k), the activation energies ( E a), and the frequency factors ( A). ZnCl 2/ 1 Cl bearing the electron-withdrawing chlorine group initiates the reaction above 80 °C, whereas ZnCl 2/ 1 OMe bearing the electron-donating methoxy group initiates the reaction above 100 °C. The E a values in the reactions with ZnCl 2/ 1 Cl and ZnCl 2/ 1 OMe were estimated to be 52.2 and 177 kJ mol −1, respectively, which agree with the latencies at ambient temperatures. The A values also differ with the catalysts (6.46 × 10 2 and 2.04 × 10 19 L mol −1 s −1 for ZnCl 2/ 1 Cl and ZnCl 2/ 1 OMe, respectively). The very high A values for the catalysts with electron-donating groups manifest the very good latencies under ambient conditions, in spite of the high activities at elevated temperatures. The coordination behavior of ZnCl 2 /1 R was evaluated by 1H NMR, 13C NMR, 15N NMR, and IR spectroscopies to understand the substituent effects.

Preparation of 1‐Arylideneamino‐ and 1‐Alkylideneamino‐3‐phenoxypropan‐2‐ol N‐Oxides—A New Type of Nitrones

The reaction of phenylglycidyl ether with hydroxylamine was evaluated, and the prepared 1‐hydroxyamino‐3‐phenoxypropan‐2‐ol was used for the 1‐arylideneamino‐ and 1‐alkylideneamino‐3‐phenoxypropan‐2‐ol N‐oxides syntheses. The title nitrones were tested as antioxidants in biological systems.

Thermokinetics of the reaction of phenyl glycidyl ether with aniline

The thermokinetic curves in the reaction of phenyl glycidyl ether with aniline were calculated for various compositions of the reaction mixture and temperatures. In addition to the main exothermic effect related to the epoxide ring opening, another exothermic effect of unknown nature was observed. The kinetic data obtained are explained in terms of structural changes caused by the self-aggregation of the reaction product molecules. The “kinetic investigation” approach provides a quantitative analysis of calorimetric data.

Reaction of glycidyl phenyl ether with imines: A model study of latent hardeners of epoxy resins in the presence of water

AbstractThe hydrolyses of several imines and their reactions with glycidyl phenyl ether were examined under highly humid conditions as a model study for the development of water‐initiated hardeners for epoxy resins. Diethyl ketone‐based imines were hydrolyzed more efficiently than methyl isobutyl ketone‐based imines. The reactions of glycidyl phenyl ether with the imines depended on their hydrolysis rates and the basicity of the amines generated from them. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 971–975, 2002

One-Step Synthesis of Polyhedral Silsesquioxanes Bearing Bulky Substituents: UV-MALDI-TOF and ESI-TOF Mass Spectrometry Characterization of Reaction Products

Fil: Fasce, Diana Patricia. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnologia de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingenieria. Instituto de Investigaciones en Ciencia y Tecnologia de Materiales; Argentina

Application of Phosphonium Ylides to Latent Catalysts. 2. Kinetic Study on the Thermal Latency of the Phosphonium Ylides in the Polyaddition of Bisphenol A Diglycidyl Ether with Bisphenol A

Substituent effects of phosphonium ylides Ph3PC(H)COR (1R) were kinetically studied in the reaction of glycidyl phenyl ether (GPE) with 2,6-dimethylphenol in the presence of the phosphonium ylide catalysts, (formylmethylene)triphenylphosphorane (1H), (acetylmethylene)triphenylphosphorane (1Me), (benzoylmethylene)triphenylphosphorane (1Ph), and (pivaloylmethylene)triphenylphosphorane (1tBu) for molecular design of excellent latent catalysts. Both the activation energy (Ea) and frequency factor (A) of the reaction increased with the bulkiness of the acyl group of 1. Further, the catalytic activity was examined in the polyaddition of bisphenol A diglycidyl ether with bisphenol A in the presence of phosphonium ylide catalysts. The catalytic activity decreased with the bulkiness of the acyl group of 1, but the latency, i.e., the starting temperature, of the epoxide conversion was little affected. On the other hand, the introduction of acetyl and cyano groups into the catalysts as the electron-withdrawing moiet...