Epoxy Kinetics

MONITORING EPOXY KINETICS WITH FLUORESCENT PROBE... 

Acrylic adhesives cure by a free radical chain growth mechanism. In contrast, epoxy and urethane adhesives cure by a step growth mechanism. This has a major impact on the cure kinetics, as well as the composition of the adhesive during cure ([9], pp. 6-9). Cyanoacrylate adhesives (such as Super Glue ) also cure by chain growth, but the mechanism is ionic with initiation by surface moisture. 

The kinetics of reaction of free radical chain reactions are complicated compared to the second-order kinetics of epoxy and urethane adhesives. Many of these complications offer practical advantages to the process of using acrylic adhesives. 

The ratio of products 15 and 16 is dependent on the structures, base, and the solvent. The kinetics of the reaction is likewise dependant on the structures and conditions of the reaction. Thus addition or cyclization can be the rate-determining step. In a particularly noteworthy study by Zimmerman and Ahramjian, it was reported that when both diastereomers of 20 were treated individually with potassium r-butoxide only as-epoxy propionate 21 was isolated. It is postulated that the cyclization is the rate-limiting step. Thus, for these substrates, the retro-aldolization/aldolization step reversible. ... 

The application of the AE reaction to kinetic resolution of racemic allylic alcohols has been extensively used for the preparation of enantiomerically enriched alcohols and allyl epoxides. Allylic alcohol 48 was obtained via kinetic resolution of the racemic secondary alcohol and utilized in the synthesis of rhozoxin D. Epoxy alcohol 49 was obtained via kinetic resolution of the enantioenriched secondary allylic alcohol (93% ee). The product epoxy alcohol was a key intermediate in the synthesis of (-)-mitralactonine. Allylic alcohol 50 was prepared via kinetic resolution of the secondary alcohol and the product utilized in the synthesis of (+)-manoalide. The mono-tosylated 3-butene-1,2-diol is a useful C4 building block and was obtained in 45% yield and in 95% ee via kinetic resolution of the racemic starting material. 

A review of epoxy-novolac reaction mechanisms and kinetics is provided by Biernath et al.85 Depending on the structures of the novolac and the epoxy, reactions have been reported to proceed through an nth-order mechanism or an autocatalytic mechanism.88-92... 

R. W. Biemath and D. S. Soane, Cure Kinetics of Epoxy Cresol Novolac Encap-sulant for Microelectronic Packaging, in Contemporary Topic in Polymer Science. Advances in New Material. Vol. 7, J. S. Salamone and J. S. Riffle (Eds.), Plenum, New York, 1992, pp. 103-160. 

Epoxidized novolacs, 411 Epoxy -phenol networks, 411-416 properties of, 413-416 Epoxy-phenolic reaction kinetics of, 413 mechanism of, 411-412 Epoxy structures, 414 e-Caprolactam, 174... 

Rozengerk, v. A. Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy Oligomers with Amines. Vol. 75, pp. 113-166. 

Figure 8. Kinetics of the photopolymerization of an epoxy diacrylate resin with and without UV absorber CO.5 % of Tinuvin 900)...

Figure 10. Kinetics of the discoloration of a 2 mm plate of stabilized PVC, with or without a 70 ym epoxy acrylate coating upon QUV aging at 40°C...

Mailhot B, Morlat-Therias S, Bussiere P-O, Gardette J-L (2005) Study of the degradation of an epoxy/amine resin, kinetics and depth-profiles. Macromol Chem Phys 206 585-591... 

A Kinetic Study of an Anhydride-Cured Epoxy Polymerization... 

The resin system selected to initiate these studies is a step-growth anhydride cured epoxy. The approach to the kinetic analysis is that which is prevalent in the chemical engineering literature on reactor design and analysis. Numerical simulations of oligomeric population density distributions approximate experimental data during the early stages of the cure. Future research will... 

In another approach, the alcohol moiety, formed by an enzymatic hydrolysis of an ester, can act as a nucleophile. In their synthesis of pityol (8-37a), a pheromone of the elm bark beetle, Faber and coworkers [17] used an enzyme-triggered reaction of the diastereomeric mixture of ( )-epoxy ester 8-35 employing an immobilized enzyme preparation (Novo SP 409) or whole lyophilized cells of Rhodococcus erythro-polis NCIMB 11540 (Scheme 8.9). As an intermediate, the enantiopure alcohol 8-36 is formed via kinetic resolution as a mixture ofdiastereomers, which leads to the diastereomeric THF derivatives pityol (8-37a) and 8-37b as a separable mixture with a... 

The kinetic resolution by etherification has also been conducted through the cyclization of epoxy aliphatic alcohols.274 In these reactions catalyzed by monomeric complex 51, the ring closure of acyclic substrates occurred with exclusive / -selectivity (Equation (74)), whereas m -openings were observed in the desymmetrization of... 

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