The Diels-Alder Reaction in Polymer Synthesis

Stille, J. K.; Harris, Frank W.; Mukamal, Harold; Rakutis, R. O.; Schilling, Curtis L.; Noren, G. K.; Reed, Joe A.

doi:10.1021/ba-1969-0091.ch041

Cited by 20 publications

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“…The use of Diels-Alder reaction in materials science is not a new research topic [16], and nowadays, it covers a significant range including polymer synthesis, pharmaceutical, and biomedical engineering [17][18][19][20][21]. In that field, the complication of considering the equilibrium reaction with the kinetic model of the Diels-Alder reaction can be often minimized, depending on the system studied and the methodology selected.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic and Kinetic Study of Diels–Alder Reaction between Furfuryl Alcohol and N-Hydroxymaleimides—An Assessment for Materials Application

2020

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The study of Diels–Alder reactions in materials science is of increasing interest. The main reason for that is the potential thermoreversibility of the reaction. Aiming to predict the behavior of a material modified with maleimido and furyl moieties, 1H NMR and UV-Vis solution studies of the Diels–Alder reaction between furfuryl alcohol and two N-hydroxymaleimides are explored in the present study. Rate constants, activation energy, entropy, and enthalpy of formation were determined from each technique for both reacting systems. Endo and exo isomers were distinguished in 1H NMR, and the transition from a kinetic, controlled Diels–Alder reaction to a thermodynamic one could be observed in the temperature range studied. A discussion on the effect of that on the application in a material was performed. The approach selected considers a simplified equilibrium of the Diels–Alder reaction as the kinetic model, allowing materials scientists to evaluate the suitability of using the reacting molecules for the creation of thermoresponsive materials. The proposed approach determines the kinetic constants without the direct influence of the equilibrium constant value, thereby allowing a more objective data analysis. The effects of the selection of kinetic model, analytical method, and data treatment are discussed.

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Section: Introductionmentioning

confidence: 99%

Thermodynamic and Kinetic Study of Diels–Alder Reaction between Furfuryl Alcohol and N-Hydroxymaleimides—An Assessment for Materials Application

2020

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“…A second approach involves using maleimide-terminated monomers (bismaleimides or BMIs) in equal molar ratios with a dinucleophile, such as a diamine, or a diene like dibenzocyclobutane (BCB) and substituted dicyclopentadienes to form the corresponding linear polyaspartimides via Michael-type addition or the polyimides via a Diels-Alder [4 + 2] cycloaddition (Table 4) (104)(105)(106)(107)(108)(109)(110)(111)(112)(113)(114)(115). Linear polyimides can be synthesized directly from the A-B maleimidobenzocyclobutane monomers (116).…”

Section: Synthesis Of Polyimides Using Imide-containing Monomersmentioning

confidence: 99%

“…These reactions proceed without volatile evolution, but undergo thermally initiated retrograde reactions that lead to change in physical properties, chemical cross-linking, and aromatization of the cyclohexene ring (BCBs). Reactions involving BMIs with dicyclopentadieneones also proceed by a cycloaddition mechanism (114,115). This has the same advantage inherent to all Diels-Alder reactions in that no volatiles are generated.…”

Section: Synthesis Of Polyimides Using Imide-containing Monomersmentioning

confidence: 99%

“…However, with these pentadieneone dieneophiles, CO is eliminated forming a cyclohexadiene moiety. The cyclohexadiene can undergo further addition reactions or aromatize with the abstraction of two hydrogen atoms, depending on the reaction conditions and the added stability of any pendent substituents (114,115). This type of chemistry can be used to create photosensitive polyimides for imaging.…”

Section: Synthesis Of Polyimides Using Imide-containing Monomersmentioning

confidence: 99%

“…Acetic anhydride (slightly over 1 equiv) is added and the mixture is heated at reflux for several hours and the crude product is isolated by water precipitation. The intermediate maleamic acid is susceptible to isomerization during cyclodehydration, resulting in the production of the less desirable acetanilide (72,115). Metal acetate catalysts have been known to increase the yields of BMI (125).…”

Section: Synthesis Of Polyimides Using Imide-containing Monomersmentioning

confidence: 99%

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Polyimides

Bryant¹

2002

Encyclopedia of Polymer Science and Technology

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Polyimides are a class of high performance polymers that contain an imide group, defined as an sp 3 nitrogen bonded to two adjacent carbonyls. This imide structure is most commonly found as part of a five‐ or six‐membered ring. Polyimides are noted for their mechanical properties, chemical resistance, and dielectric strength. They exist as thermoplastics and thermosets. Polyimides are used as hot melt adhesives, matrix resins for composites, dielectric films, photoimageable coatings, flex circuits, foams, wire insulation, thin‐walled tubing, molding resins, and high performance bushings and seals. Products that compete with polyimides for niche applications include aerospace epoxies (Dow, Ciba, and Shell), cyanate resins (Dow), polysulfones (Solvay), filled polycarbonates and polyesters (Dow, Amoco, and GE), polybenzimidazoles (Hoechst‐Celanese), and some high T g filled phenolics. Although polyimides command a premium price, their versatility, reliability, and demonstrated performance make them suitable for use in high performance applications where failure and replacement costs are high.

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Polyimides

Takekoshi¹

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Polyimides are high performance polymers employed as key materials in advanced industrial applications, including aerospace, electrical, and electronic engineering. Polyimides are capable of functioning at high temperature and in oxidative environments, and have outstanding mechanical strength, excellent electrical properties, and wide ranging chemical resistance. One of the advantageous characteristics of polyimides over other high temperature polymers is their processibility through soluble intermediates. Polyimide polymerization is a thermodynamically driven condensation reaction and can be performed in a simple manner, including in situ polymerization. It is also a versatile system in terms of synthesizing wide varieties of copolymer compositions for the required properties. In this article, various synthetic methods for polyimides, and properties and applications of principal commercial polyimides, are reviewed. Advances in the chemistry and applications of polyimides are also described.

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The Diels-Alder Reaction in Polymer Synthesis

Cited by 20 publications

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Thermodynamic and Kinetic Study of Diels–Alder Reaction between Furfuryl Alcohol and N-Hydroxymaleimides—An Assessment for Materials Application

Thermodynamic and Kinetic Study of Diels–Alder Reaction between Furfuryl Alcohol and N-Hydroxymaleimides—An Assessment for Materials Application

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