Preparation and properties of poly‐p‐xylylene

Abstract

The preparation of poly‐p‐xylylene, , in 24–26% yield, by pyrolysis of p‐xylene, is described in detail. The nature and amount of by‐products of the pyrolysis were determined. The physical appearance and the following properties and reactions of the polymer are described: x‐ray diffraction, crystallinity, optical constants, infrared absorption spectrum, degradation by autoxidation in solvents and by pyrolysis, dielectric constant and loss, sulfonation and chlorination. The significance of this data is discussed relative to an understanding of the mode of formation and the structure of the polymer.

Polymerization of chloro-p-xylylenes, quantum-chemical study

“…The so changed monomers can still polymerize in relatively low temperatures. On the other hand, such high reactivity of those polymers is basically a drawback in copolymerization processes, for instance with styrene [15]. This is caused by the fact that the vinyl and etin polymerizations are characterized generally by higher reaction barriers; many such processes require catalizers.…”

“…A similar variation of monomer reactivity can be observed in their copolymerization reaction with vinyl compounds. No copolymerization of styrene or other vinyl monomer and p-xylylene was observed when they were passed together through the pyrolysis zone [15]. P-xylylene is too reactive for cross reaction with styrene [15].…”

“…No copolymerization of styrene or other vinyl monomer and p-xylylene was observed when they were passed together through the pyrolysis zone [15]. P-xylylene is too reactive for cross reaction with styrene [15]. On the other hand, both 7,7,8,8-tetrachloro-pxylylene and 2,5,7,7,8,8-hexachloro-p-xylylene copolymerize with various vinyl monomers such as styrene, vinyl acetate, acrylonitryle and methyl methacrylate [31].…”

“…For effective copolymerization processes this fact is basically a drawback and for instance the copolymerization with styrene doesn’t go at all (Corley et al J Pol Sc 13(68):137–156, [15]). Substitution of terminal hydrogen atoms by chlorine atoms reduces reactivity dramatically.…”

First polyrecombination reaction via atom transfer radical coupling (ATRC), a new way for the synthesis of poly(p-xylylene)

“…It was first reported by Szwarc [15,16] by chemical vapor polymerization (CVP) of p-xylene or di-p-xylylene (2,2-p-cyclophane) [17]. The synthesis of PPX is usually accomplished by polyreaction of 1,4-quinondimethanes, although the routes for generating 1,4-quinondimethanes can be very different [18,19]. Other methods, starting from α,α -dibromo-or dichloroxylene were also reported in the literature.…”