Polymers, formaldehyde Structure

Amino resins are those polymers prepared by reaction of either urea or melamine with formaldehyde. In both cases the product that results from the reaction has a well crosslinked network structure, and hence is a thermoset polymer. The structures of the two parent amino compounds are shown in Figure 1.1. 

It should not be taken for granted that all polymers that are defined as condensation polymers by Carothers classification will also be so defined by a consideration of the polymer chain structure. Some condensation polymers do not contain functional groups such as ester or amide in the polymer chain. An example is the phenol-formaldehyde polymers produced by the reaction of phenol (or substituted phenols) with formaldehyde... 

Acetal resins n. High molecular weight, stable, linear polymers of formaldehyde structurally, an oxygen atom joins the repeating units in an ether rather than ester-type link. These also include butyrals. Strong AB (2000) Plastics materials and processing. Prentice-Hall, Columbus, OH. 

As mentioned earlier, polymers of formaldehyde are described in the next section. Polymers of higher aliphatic aldehydes and ketones have been extensively investigated but, in general, they do not have the stability necessary for commercial development. For example, acetaldehyde may be polymerized using organometallic initiators at low temperatures, e.g., triethylaluminium at —78 C in this case crystalline isotactic polymer is obtained. Also, the polymerization of acetaldehyde may be effected with cationic initiators at low temperatures (e.g., aluminium chloride at —65°C) or with metal oxides at low temperatures (e.g., alumina at —70°C) in these cases amorphous atactic polymer is obtained. The tacticity of polyacetaldehyde arises because the polymer comprises structural units which contain an asymmetric carbon atom ... 

Open pore urea-formaldehyde structures have unique properties, and their spherical and pore sizes can be controlled to make them suitable for many applications. Filtration structures, chromatographic columns, porous urea-formaldehyde pigmented polystyrene, smog dispersal agents, moisture retentive fertilizers, fruit coatings, and porous polymer-bound multicomponent corrosion inhibitors have been prepared. Development of technologies based on open pore urea-formaldehyde structures is a distinct possibility. 

Some commercially important cross-linked polymers go virtually without names. These are heavily and randomly cross-linked polymers which are insoluble and infusible and therefore widely used in the manufacture of such molded items as automobile and household appliance parts. These materials are called resins and, at best, are named by specifying the monomers which go into their production. Often even this information is sketchy. Examples of this situation are provided by phenol-formaldehyde and urea-formaldehyde resins, for which typical structures are given by structures [IV] and [V], respectively ... 

The less simple polymers (like the epoxies, the polyesters and the formaldehyde-based resins) are networks each chain is cross-linked in many places to other chains, so that, if stretched out, the array would look like a piece of Belgian lace, somehow woven in three dimensions. These are the thermosets if heated, the structure softens but it does not melt the cross-links prevent viscous flow. Thermosets are usually a bit stiffer than amorphous thermoplastics because of the cross-links, but they cannot easily be crystallised or oriented, so there is less scope for changing their properties by processing. 

Polymerization and curing rates of novolacs depend strongly on the acidity of the reaction mixture. Fig. 16 depicts the general pH dependence. Fig. 17 shows a partial structure for a hexa-cured novolac. Incorporation of amine is widely, though not universally, reported in hexa-cured novolac structures. In addition to the structure shown in Fig. 17, A, A -dibenzyl and A, A, A -tribenzylamine linkages have been reported [185-192]. The main by-products of hexa-curing conditions are water and ammonia, though formaldehyde is also produced. The structure and abundance of the amino portions of the cured polymer vary considerably with conditions. 

The smoking salons of the Hindenburg and other hydrogen-filled dirigibles of Ihe 1930s were insulated with urea-formaldehyde polymer foams. The structure of this polymer is highly cross-linked, like that of Bakelite (Section 31.5). Propose a structure. 

The final structure of resins produced depends on the reaction condition. Formaldehyde to phenol (F/P) and hydroxyl to phenol (OH/P) molar ratios as well as ruction temperahne were the most important parameters in synthesis of resols. In this study, the effect of F/P and OH/P wt%, and reaction temperature on the chemical structure (mono-, di- and trisubstitution of methyrol group, methylene bridge, phenolic hemiformals, etc.) was studied utilizing a two-level full factorial experimental design. The result obtained may be applied to control the physical and chemical properties of pre-polymer. 

If the polymer is hard, insoluble, and infusible without decomposition, and if it refuses to swell greatly in any solvent, it may be assumed either that it is highly crystalline, with a melting point above its decomposition temperature, or that it possesses a closely interconnected network structure (e.g., as in a highly reacted glyceryl phthalate or a phenol-formaldehyde polymer). Differentiation between these possibilities is feasible on the basis of X-ray diffraction. 

Polymer (184) has a network structure and was obtained by reaction of dibenzo-18-crown-6 with formaldehyde in formic acid. Amongst the alkali metal ions, it selectively captures K+ and Cs+ from methanol or methanol/water. A related polymeric product has been reported (as a gel) from the reaction of this crown with formaldehyde in chloroform using sulfuric acid as catalyst (Davydova, Baravanov, Apymova Prata, 1975). 

As a molar excess of formaldehyde is used to produce resins, the polymers will get terminated predominantly by methyl groups. The general structure of the methylene-containing polymers may therefore by put as follows ... 

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