Competitive amidation of sebacoyl chloride with mixtures of hexamethylenediamine and 1,1′‐bis(β‐aminoethyl) ferrocene

Abstract

We recently reported the synthesis of the monomer l,l'-bis(/3-aminoethy1)ferrocene (1) and its polymerization with diacid chlorides via interfacial condensation techniques to form polyamides.' CH ,CH,NH , ?Fe 1In the present study, it was of interest to determine the relative reactivities of hexamethylenediamine and 1,l'-bis( P-aminoethy1)ferrocene (1) vis-a-vis sebacoyl chloride. Monomer 1 does contain aliphatic amine functional groups which are not hindered in their reactivities, sterically or electronically, by the ferrocene nucleus.' However the diffusion of 1 could be affected by its relative bulk and rigidity compared to the greater flexibility of the methylene groups in hexamethylenediamine.Korshak and coworkers' had reported the formation of mixed polyamides by interfacial polymerization with mixtures of various diamines. Interfacial polymerization was conducted with adipoyl chloride and mixtures of ethylenediamine, hexamethylenediamine, or m-phenylenediamine in a benzenewater system. These investigators demonstrated that mixed polyamides and not mixtures of homogeneous products were formed. In the first stages of the reaction the composition of the mixed polyamides found a t the interface differed from the composition of the original mixture, and was determined by the diffusion of the diamines into the organic phase. The reactivities of the diamines were considered to be of only secondary importance. RESULTS AND DISCUSSIONS Blends of 6,lO Nylon and FcJO Organometallic PolyamideAt the outset it should be clarified, that by analogy to the nomenclature for nylons, it was decided to term the polyamide obtained from sebacoyl chloride and 1,l'-bis( /3-aminoethy1)ferrocene as Fc,lO organometallic polyamide (nylon).

Organometallic Polymers of the Transition Metals

“…An alternative route to ferrocenebased polymers involved the reaction of 1,1 0 -bis(baminoethyl)ferrocene with dimethylbis(4-chlorocarbonylphenyl)silane. [127] Polyamides, polyureas, polyurethanes and polyesters were investigated by Rausch and coworkers in the 1980s, [129][130][131][132][133] and research into these classes of polymers continues to progress. [134][135][136][137][138] It was found that polymers prepared with a-functionalized ferrocenes often had lower molecular weights and displayed poorer stability due to formation of the a-ferrocenyl carbonium ion and steric factors.…”

Photochemically Reactive Polymers. Identification of the Products Formed in the Photochemical Degradation of Polyurethanes That Contain (C5H4R)(CO)3Mo−Mo(CO)3(C5H4R) Units along Their Backbones

“…Our syntheses of metal−metal-bond-containing polymers use metal−metal-bonded organometallic dimers with functionally substituted cyclopentadienyl ligands, a synthetic method borrowed from earlier work on polyferrocenes. − An example of a polyurethane synthesis is shown in eq 1 . Thus far, polyurethanes, polyureas, polyethers, polyvinyls, polyamides, and several types of copolymers with metal−metal bonds along the backbone have been synthesized .…”