Phenylglycidyl ether

Epichlorohydrin, propylglycidyl ether, allylglycidyl ether, phe-noxy-2-propanone, and phenylglycidyl ether... 

Terrill JB, Lee KP The inhalation toxicity of phenylglycidyl ether. I. 90-day inhalation study. Toxicol Appl Pharmacol 42 263-269, 1977... 

Lee KP, Schneider PW, Trochimowicz HJ Morphological expression of glandular differentiation in the epidermoid nasal carcinomas induced by phenylglycidyl ether inhalation. Am J Pathol m-.m-m, 1983... 

Gaul and Carr in 198 3 50) characterized an oxirane species which is reacted with Al(acac)3 and diphenylmethyl silanol. C-13, Si-29 and Al-27 solution NMR was used along with model compounds to characterize the above reaction. The systems studied were 1,2-epoxybutane (1,2-EB), cyclohexene oxide and phenylglycidyl ether with Al(acac)3 and diphenylmethyl silanol (DPMS). 

Also phenylglycidyl ether (PhGE) reacts with aniline under these conditions 28). However, the initial reaction rate is proportional to the square of the aniline concentration. The presence of even small amounts of moisture decreases the order of the reaction with respect to amine concentration. The quadratic dependence of the reac-... 

This Scheme is to be supplemented with complexing reactions between all the proton donors in the system and electron donor atoms in the starting components (for example, oxygen atom in the PhO ether bond in a phenylglycidyl ether molecule) and the corresponding reaction products. 

Fig. 2. Dependence of heat release on conversion in the reaction of phenylglycidyl ether with aniline...

A combined application of direct calorimetric measurements and thermochemical investigations has made possible to obtain a number of important thermochemical quantities characterizing the interaction of the N—H bond of the amine with the epoxy ring 53). Combustion and evaporation enthalpies of phenylglycidyl ether and its condensation products with aniline and butylamine have been determined. Standard enthalpies of the formation of these compounds, strain energies of the epoxy ring in the phenylglycidyl ether molecule and — AH values for the three-phase states, which are most important for the determination of the true thermodynamic reaction characteristics, have been estimated. 

Fig. 4. Kinetics of phenylglycidyl ether consumption (1) and relative viscosity changes (2) in the reaction of phenylglycidyl ether (Eo = 4.4 mol 1 1) with aniline (Ao = 4.4 mol l-1) at 363 K 441...

Fig. 5. Dependence of limiting conversion of phenylglycidyl ether on the ratio of reagents (I) and dilution with o-dichlorobenzene (2) in the interaction with aniline (A) at 363 K.431...

Fig. 9. Kinetic curves of phenylglycidyl ether polymerization in chlorobenzene solution under the action of dimethylbenzylamine and in the presence of isopropyl alcohol at 343 K 14). 1 E0 = A3 0 = 1.75 mol r, 2H0 = 0. The introduction of fresh monomer is shown by an arrow...

The structure of the epoxy polymers formed in the curing process has been thoroughly investigated using phenylglycidyl ether polymerization as an example. 

Fig. 10. Kinetic curves of phenylglycidyl ether polymerization (7.0 mol I-1) under the action of dimethylbenzylamine (0.25 mol 1 ) in the presence of isopropyl alcohol (0.25 mol I"1) and in the accumulation of hydroxyl and vinyl groups in the system at 353 K 149 1501...

Molecular-mass characteristics of these polymers are very interesting I4,20,136, i54. ns. i58) oligomer with a mean degree of polymerization equal to ca. 5 has been formed by polymerization of phenylglycidyl ether. Its molecular-mass characteristics are extremely insensitive either to monomer conversion (Table 9) or to variations of polymerization conditions (Table 10). 

Table 9. Dependence of the molecular-mass-distribution of phenylglycidyl ether oligomers on conversion...

Table 10. Dependence of the molecular-mass distribution of the oligomers on the polymerization conditions of phenylglycidyl ether (PhGE) under the action of dimethylbenzylamine (DMBA) and isopropyl alcohol (IPA) 152 1S8>...

Fig. 12. Kinetic curve of phenylglycidyl ether polymerization (see Fig. 10) according to eq. (35) 141...

Fig. 13. Dependence of the rate of hydroxyl groups accumulation in the polymerization of phenylglycidyl ether (7 mol I1) and in the presence ofdimethylbenzylamine(0.25 mol I 1) and amyl alcohol (0.25 mol I-1) at 343 K on the concentration of the active growing sites1501...

Fig. 14. Kinetic curves of phenylglycidyl ether polymerization (6.67 mol I-1) under the action of dimethylamine (0.66 moll-1) at 343 K. 1 Pure (chromatography grade) undried phenylglycidyl ether, 2 dried with calcium hydride and dosed in dry argon, 3 precision drying and purification of the reagents in the reaction vessels, reagent dosed in vacuo 1+91...

The estimation of the reactivities of the free ions and ion pairs directly in the polymerization reaction of phenylglycidyl ether under the action of dimethylbenzylamine in the presence of isopropyl alcohol at 343 K 15l) gave k = 5.6 1 mol-1 s-1 and k = 0.71 mol1 s 1. The values of the bimolecular rate constants are given here considering the fact that the activated molecules of the monomer (its complexes with alcohol) take part in the chain propagation reaction. 

Kinetic curves of phenylglycidyl ether consumption in the reaction with aniline in the presence of dimethylbenzylamine (DMBA) are presented in Fig. 15 a. As can be seen from this figure, addition of DMBA considerably increase the rate of monomer consumption in the initial and especially in the later stages of the reaction. The amount of the monomer consumed during polycondensation and polymerization can be readily determined by a parallel determination of the aniline consumption (Fig. 15 b). 

Fig. ISa and b. Kinetic curves of the consumption of phenylglycidyl ether (a) and aniline (b) in the presence of dimethylbenzylamine, mol 1 ...

Table 3. Hammett reaction constants q for the copolymerization of p-N02, p-C02CH3, p-Cl, p-H, p-CHj, and p-OCH3 substituted phenylglycidyl ethers with hexahydrophthalic anhydride initiated with tri-n-butylamine ...

Another reactivity order is reported for the copolymerization of anhydrides with phenylglycidyl ether and with 3,3-bis-chloromethyloxacyclobutane 41) glutaric > phthalic > succinic anhydrides. 

The first scheme of the reaction between acetic anhydride and phenylglycidyl ether initiated by potassium acetate was proposed by Schechter and Wynstra 26)... 

Tanaka and Kakiuchi52 > analyzed the conversion curves for the copolymerization of substituted phenylglycidyl ethers with hexahydrophthalic anhydride and found a first-order dependence with respect to the initiator at the maximum reaction rate (Eq. (80)), and second-order kinetics for the region of initiation (Eq. (81)). 

Second-order kinetics with respect to the amine and epoxide was also found by Antipova et al. 65) for the curing of epoxy resins with hexahydrophthalic anhydride, by Sorokin et al.321 for the reaction of phenylglycidyl ether with phthalic anhydride in the presence of butanol, Luston and Manasek 45 74) for the copolymerization of 2-hydroxy-4-(2,3-epoxypropoxy)benzophenone with phthalic anhydride in the absence or in the presence of proton donors, and Kudyakov et al. 98) for the curing of epoxy resins with maleic anhydride. 

Boos and Flauschildt90) obtained for the model copolymerization of phenylglycidyl ether with hexahydrophthalic anhydride activation energies of 96 kJ/mol up to 75% conversion and 27 kJ/mol for higher conversions. Frequency factors are also very different (log A = 13.7 and 5.5, respectively). The frequency factors as well as the temperature coefficients of the solution viscosities depended on the initiator concentration. The activation energy determined by the same authors 90) for the curing of epoxy resins at conversions lower than 75% was 86.4 kJ/mol and the frequency factor log A = 11.8 whereas at higher conversions these values were not obtained. 

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