Addition-curing norbornene

Radical Polymerization of exo and endo iV-Phenyl-5-norbornene-2,3-dicarboximides as Models for Addition-Curing Norbornene End-Capped Polyimides1... 

Commercial grades of ethylene-propylene copolymers (EPR) contain 60-75 mol% of ethylene to minimize crystallization. The addition of a third monomer, such as 1,4-hexadiene, dicyclopentadiene, or 5-ethylidene-2-norbornene, produces generally amorphous faster-curing elastomers. A large number of such terpolymers, referred to as EPDM, is available commercially. Their properties, performance, and response to radiation vary considerably depending on macrostructure, ethylene/propylene ratio, as well as on the type, amount, and distribution of the third monomer. 

Wong and coworkers. [82, 83] used solution and solid-state NMR to study the cure of the norbornene end-capped poly(imide)s 2NE/DDM and PMR-15. At lower cure temperatures, exo-endo isomerization was observed to be a major product [84]. Loss of cyclopentadiene was suggested to result in initiation of the partner maleimide, as well as Diels-Alder addition of cyclopentadiene with norbornene. There was no evidence of internal double bonds formed by incorporation of the cyclopentadiene into the polymer backbone. The solid-state spectra were very poorly resolved, but did allow confirmation of the mechanism of reaction [83]. Spectra obtained at higher fields did not show improved resolution, indicating that the dominant mechanism for line-broadening in these materials is the dispersion of isotropic chemical shifts resulting from frozen conformations. In later work, Milhourat-Hammadi and coworkers [84, 85] reported solution-state and NMR studies of PMR-15 prepolymers. 

Properties of cured heaUng monomers, and consequently the quaUty of heaUng, can be altered by incorporating additives to the heaUng monomers (Table 10.2). Bis-norbornene and l,4 di-norbornenylbenzene cross-linkers have been shown to... 

The diene ethylidiene norbornene in Vistalon EPDM allows sulfur vulcanization (see Table 3.12). 1,4-Hexadiene and dicyclopentadiene (DCPD) are also used as curing agents.The completely saturated polymer backbone precludes the need for antioxidants that can bleed to the surface (bloom) of the finished product and cause staining. Saturation provides inherent ozone and weather resistance, good thermal properties, and a low compression set. Saturation also allows a relatively high-volume addition of low-cost fillers and oils in compounds while retaining a high level of mechanical properties. The ethylene/propylene monomer ratio also affects the properties. 

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