Trioxane, formaldehyde polymer Structure

The Celanese route for the production of polyacetal yields a more stable copolymer product via the reaction of trioxane, a cyclic trimer of formaldehyde, and a cyclic ether, such as ethylene oxide or 1,3 dioxolane. The structures of these monomers are shown in Figure 3.25. The polymer structure is represented in Figure 3.26. 

Commercial polymers of formaldehyde are also produced using cationic polymerization. The polymer is produced by ring opening of trioxane. Since the polyacetal, POM, is not thermally stable, the hydroxyl groups are esterified (capped) by acetic anhydride (structure 5.22). These polymers are also called poly(methylene oxides). The commercial polymer is a... 

Acetal resins are those homopolymers (melting point ca. 175°C, density ca. 1.41) and copolymers (melting point ca. 165°C, density ca. 1.42) where the backbone or main structural chain is completely or essentially composed of repeating oxymethylene units (-CH20-)n. The polymers are derived chiefly from formaldehyde (methanal, CH2=0), either directly or through its cyclic trimer, trioxane or 1,3,5-trioxacyclohexane. 

The polymer F of formaldehyde is called polyoxymethylene or paraformaldehyde. It contains two OH groups, one at each end of the molecule, but these are omitted for clarity in the structural formula shown in Figure 7.14. This shows that one molecule of water, which is present everywhere even in the most careful work, has been incorporated. If these terminal OH groups are functionalized, paraformaldehyde can be used as plastic. When paraformaldehyde is heated with acid, it is transformed (entropy gain) into the cyclic trimer B from Figure 7.14, which is called 1,3,5-trioxane. 

Hg. 4.12 The 2D and 3D structures of formaldehyde in a number of different disguises gas (a), aqueous solution (formaldehyde hydrate, b), solid trimer (trioxane, c), solid polymer (paraformaldehyde, d) and the odor substance of shiitake mushrooms (lenthionine, e). (Authors own work)... 

The most important polyacetal is obtained from the polymerization of either formaldehyde or trioxane, its cyclic trimer. This polyacetal is called poly(oxy-methylene), and its acronym is POM. Trioxane can possibly be copolymerized by cationic process with other heterocycles, particularly ethylene oxide, leading to polymer chains having structural regularity less than that of the conventional POM and yielding less crystalline and less cohesive materials. 

Acetal homopolymer is a highly crystalline thermoplastic manufactured by polymerization of formaldehyde and capping the two ends of the polymer chain with acetate groups (Table 6.2). It is called polyoxymethylene (POM) and has a backbone consisted of repeating —CH2O—units. Acetal copolymers are produced by copolymerization of trioxane and small amounts of a comonomer. The comonomer randomly distributes carbon—carbon bonds in the polymer chain, which stabilizes the resin against environmental degradation. The low cost of acetals compared to other polymers with similar performance and their mechanical, chemical, and electrical properties, allows them to replace metal and other structural materials in many applications. 

---