Trioxane, formaldehyde polymer

In addition to the usual polymer-monomer propagation-depropagation equilibrium that may he present, trioxane polymerization proceeds with the occurrence of a polymer-formaldehyde equilibrium ... 

The polymer, sym-Trioxane, also known as crTrioxymethylene, Mela formaldehyde,... 

Formaldehyde (mp = —I18 C, bp1-01J => 19 C, dl201131 = 0.8153) is normally a gas. It is chiefly marketed in the form of aqueous solutions of formalin containing 37 to 60 per cent weight of the pure product. These solutions tend to polymerize, even more easily in high concentrations. Hence if they are not used immediately, they must be stabilized by the addition of methanol (7 to 15 per cent weight). A small amount of formaldehyde is sold in the form of solid polymers (paraldehyde, trioxane). 

Many aldehydes ttimeiize in acidic conditions. Paraldehyde and many other trimers fail to undergo further polymerizations to high molecular weight, linear polymers. The trimer of formaldehyde, trioxane, however, is unique. It polymerizes by a mechanism of ring-opening polymerization. This... 

The term "acetal resins" commonly denotes the family of homopolymers and copolymers whose main chains are completely or essentially composed of repeating oxymethylene units (—CH2—O—). The polymers are derived chiefly from formaldehyde or methanal [50-00-00] either directly or through its cychc trimer, trioxane or 1,3,5-trioxacyclohexane [110-88-3]. 

The details of the commercial preparation of acetal homo- and copolymers are discussed later. One aspect of the polymerisation so pervades the chemistry of the resulting polymers that familiarity with it is a prerequisite for understanding the chemistry of the polymers, the often subde differences between homo- and copolymers, and the difficulties which had to be overcome to make the polymers commercially useful. The ionic polymerisations of formaldehyde and trioxane are equiUbrium reactions. Unless suitable measures are taken, polymer will begin to revert to monomeric formaldehyde at processing temperatures by depolymerisation (called unsipping) which begins at chain ends. 

When the equihbrium formaldehyde concentration is reached, polymer begins to precipitate. Further polymerisation takes place in trioxane solution and, more importantly, at the surface of precipitated polymer. 

The enthalpy of the copolymerization of trioxane is such that bulk polymerization is feasible. For production, molten trioxane, initiator, and comonomer are fed to the reactor a chain-transfer agent is in eluded if desired. Polymerization proceeds in bulk with precipitation of polymer and the reactor must supply enough shearing to continually break up the polymer bed, reduce particle size, and provide good heat transfer. The mixing requirements for the bulk polymerization of trioxane have been reviewed (22). Raw copolymer is obtained as fine emmb or flake containing imbibed formaldehyde and trioxane which are substantially removed in subsequent treatments which may be combined with removal of unstable end groups. 

Paraformaldehyde [30525-89-4] is a mixture of polyoxymethylene glycols, H0(CH20) H, with n from 8 to as much as 100. It is commercially available as a powder (95%) and as flake (91%). The remainder is a mixture of water and methanol. Paraformaldehyde is an unstable polymer that easily regenerates formaldehyde in solution. Under alkaline conditions, the chains depolymerize from the ends, whereas in acid solution the chains are randomly cleaved (17). Paraformaldehyde is often used when the presence of a large amount of water should be avoided as in the preparation of alkylated amino resins for coatings. Formaldehyde may also exist in the form of the cycHc trimer trioxane [110-88-3]. This is a fairly stable compound that does not easily release formaldehyde, hence it is not used as a source of formaldehyde for making amino resins. 

The polymer also can be made from trioxane (the trimer of formaldehyde), usually as a copolymer with ethylene oxide. The —CH2CH2— fragments in the copolymer chain prevent depolymerization acetal copolymer was developed by Celanese (10). 

Formaldehyde is a gas with a boiling point of -21 °C. It is usually supplied as a stabilised aqueous solution ( 40% formaldehyde) known as formalin. When formalin is used as the source of the aldehyde, impurities present generally include water, methanol, formic acid, methylal, methyl formate and carbon dioxide. The first three of these impurities interfere with polymerisation reactions and need to be removed as much as possible. In commercial polymerisation the low polymers trioxane and paraformaldehyde are convenient sources of formaldehyde since they can be obtained in a greater state of purity. 

The cyclic trimer (trioxane) and tetramer are obtained by a trace of sulphuric acid acting on hot formaldehyde vapour (i) Figure 19.1). Linear polymers with degrees of polymerisation of about 50 and a terminal hydroxyl group are obtained by evaporation of aqueous solutions of formaldehyde (ii). In the presence of strong acid the average chain length may be doubled. Evaporation of methanol solution leads to products of type (iii). 

Ring opening polymerization may also occur by an addition chain reaction. For example, a ring opening reaction polymerizes trioxane to a polyacetal in the presence of an acid catalyst. Formaldehyde also produces the same polymer ... 

When catalyzed by acids, low molecular weight aldehydes add to each other to give cyclic acetals, the most common product being the trimer. The cyclic trimer of formaldehyde is called trioxane, and that of acetaldehyde is known as paraldehyde. Under certain conditions, it is possible to get tetramers or dimers. Aldehydes can also polymerize to linear polymers, but here a small amount of water is required to form hemiacetal groups at the ends of the chains. The linear polymer formed from formaldehyde is called paraformaldehyde. Since trimers and polymers of aldehydes are acetals, they are stable to bases but can be hydrolyzed by acids. Because formaldehyde and acetaldehyde have low boiling points, it is often convenient to use them in the form of their trimers or polymers. 

Because of their anomolous behaviour 1,3,5-trioxan and higher polymers of formaldehyde are excluded from the present discussion, unless they are mentioned specifically. 

The formaldehyde process is an air oxidation of methanol, CH3OH, which has water as a by-product. Formaldehyde is a gas at room temperature, but is usually handled either as a water solution called formalin or as polymers called paraformaldehyde and trioxane. Both are readily converted back ro formaldehyde. Some uses of formaldehyde are the manufacture of polymer resins and as a germicide. 

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... 

Both liquid and gaseous formaldehyde polymerize readily at low temperatures and can be kept in the pure monomeric state only for a limited time. Because of these facts, formaldehyde is sold and transferred either in solution or in polymerized form, such as paraformaldehyde and trioxane, described here under Formaldehyde polymers Commercial, 37% solution of formaldehyde (So-called Methanol-free)... 

All of these polymers are linear with the exception of sym-trioxane [frtrioxymethylene) (HCHO)3] and tetraoxymelhylene HCHO)4, both of which are true polyoxymethylenes, although they are not prepd by the polymerization of monomeric formaldehyde... 

By organic chemistry formalism, polyacetals are reaction products of aldehydes with polyhydric alcohols. Polymers generated from aldehydes, however, either via cationic or anionic polymerization are generally known as polyacetals because of repeating acetal linkages. Formaldehyde polymers, which are commercially known as acetal resins, are produced by the cationic ring opening polymerization of the cyclic trimer of formaldehyde, viz., trioxane [29-30] (Fig. 1.5). 

Starting ingredients may be formaldehyde or the cyclic trimer rrioxane, CH2OCH2OCH2O. Both form polymers of similar properties. Boron trifluoride of other Lewis acids are used to promote polymerization where trioxane is the raw material. 

The copolymerization of trioxane with cyclic ethers or formals is accomplished with cationic initiators such as boron trifluoride dibutyl etherate. Polymerization by ring opening of the six-membered ring to form high molecular weight polymer does not commence immediately upon mixing monomer and initiator. Usually, an induction period is observed during which an equilibrium concentration of formaldehyde is produced. 

When the equilibrium formaldehyde concentration is reached, the polymer begins to precipitate and further polymerization takes place in trioxane... 

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. 

Tn the cationic polymerization and copolymerization of trioxane in the - melt or in solution, an induction period usually exists, during which no solid polymer is formed and the reaction medium remains clear. Nevertheless, reactions are known to occur during this period. By using BF3 or an ether ate as catalyst, in homopolymerization, Kern and Jaacks (I) reported the formation of formaldehyde via depolymerization of polyoxymethylene cations. 

This method is not affected by the side reactions described above. Elimination and addition of formaldehyde as well as cleavage of oxacyclic compounds and chain transfer by polymer regenerate predominantly Pi+, the desired active center. As noted above, fi is the more important reactivity ratio in copolymerizations of dioxolane with a large excess of trioxane. The value of can be determined conveniently by the de-... 

The difference in formaldehyde equilibrium concentration between homogeneous and heterogeneous polymerization is large enough to indicate a difference in the physical state of cationic chain ends in the dissolved and in the crystalline polymer. Thus, Model B is ruled out. In the homopolymerization of trioxane and in the heterogeneous copolymerization with small amounts of dioxolane the active centers of chains which have precipitated from the solution predominantly are directly on the crystal surface (Model A). According to Wunderlich (20, 21), this is the first case in addition polymerization where Model A—simultaneous polymerization and crystallization—has been proved experimentally. 

Formaldehyde and acetaldehyde are the most common aldehydes. Formaldehyde is a gas at room temperature, so it is often stored and used as a 40% aqueous solution called formalin. When dry formaldehyde is needed, it can be generated by heating one of its solid derivatives, usually trioxane or paraformaldehyde. Trioxane is a cyclic trimer, containing three formaldehyde units. Paraformaldehyde is a linear polymer,... 

Trioxane is not a good source of formaldehyde as it is very stable but the two other solids are good sources. Both paraformaldehyde and, more obviously, polyoxymethylene are polymers. Each molecule of either polymer consists of a large number of formaldehyde molecules reacted together. 

Trioxane is formed when the trimer cyclizes instead of continuing to polymerize. All the oligomers and polymers of formaldehyde have this potential as there is a hemiacetal group at each... 

Experiments with paraformaldehyde were unsuccessful because it was found that when these additives were mixed with hydrazine perchlorate the mixture became yellow, and the consistency changed from that of the original powders to that of a dough. S-trioxane, a more stable formaldehyde polymer than paraformaldehyde, gave a less reactive mixture than paraformaldehyde, but the results were still unsatisfactory. Delrin, a stabilized formaldehyde polymer, proved even less reactive than S-trioxane. Magnesium oxide was added to hydrazine perchlorate-Delrin mixtures, on the theory that acidity in the hydrazine perchlorate might be... 

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