Syntheses of Macromolecular Compounds

The variety of reaction possibilities implies a new science—the science of mechanochemistry. Starting with just such results, we have achieved some new syntheses in the domain of macromolecular compounds—namely mechanochemical polycondensation and complexation. 

Since the last review of catalysis by macromolecules well over 1000 publications relevant to this topic have appeared. The present review is therefore necessarily selective. There have been several reviews on the syntheses and aizyme-like functions of macromolecular compounds. ... 

Sulfur Dyes. These dyes are synthesized by heating aromatic amines, phenols, or nitro compounds with sulfur or, more usually, alkah polysulfides. Unlike most other dye types, it is not easy to define a chromogen for the sulfur dyes (qv). It is likely that they consist of macromolecular stmctures of the phenothiazone-thianthrone type (72), in which the sulfur is present as (sulfide) bridging links and thiazine groups (1). 

Finally, it should be mentioned that there exist two other routes for the synthesis of copolymers. First the partial chemical conversion of homopolymers (see Sect. 5.1), for example, the partial hydrolysis of poly(vinyl acetate). Secondly, by homopolymerization of correspondingly built monomers. An example for these macromolecular compounds, sometimes called pseudo-copolymers, is the alternating copolymer of formaldehyde and ethylene oxide synthesized by ringopening polymerization of 1,3-dioxolane. 

The pyrolysis properties of four model compounds were examined. Their molecular structures are shown in Table II. The three and four-ring molecules, containing a benzo [b] thiophenic unit were synthesized by Dr. Cagniant (L.S.C.O., Metz University). A polycyclohexanesulfide is an aliphatic sulfide synthesized by Dr. N. Spassky (Laboratory of Macromolecular Chemistry, Paris VI University). Polymeric aromatic sulfide was represented by a polybenzosulfide provided by Philips Petroleum. 

Two new catalytic reactions occurring between the same parent substances have been developed since 1984, i.e. the silylative coupling (dehydrogenative or trans-silylalion, silyl group transfer) and cross-metathesis of alkenes with vinylsilicon compounds. They make it possible to synthesize molecular and macromolecular compounds with vinylsilicon functionality. 

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