Melamine-formaldehyde polymers development

Melamine was first isolated by Liebig in 1834 from the mixture obtained by heating ammonium thiocyanate. A technically feasible route to melamine was developed in 1935 by Ciba AG (Switzerland) and at the same time Henkel patented the production of resins from melamine and formaldehyde. In general, melamine-formaldehyde polymers resemble urea-formaldehyde pol)miers but they have improved resistance to heat and water. The two materials have therefore found application in similar areas, melamine-formaldehyde resins now being widely used in the production of moulding powders, laminates, adhesives, surface coatings and textile finishes. 

Data of low-temperature nitrogen adsorption were used to evaluate the parameters characterizing the pore structure of the obtained polymeric materials in dry state. The BET specific surface area, Sbet, and the total pore volume, V, were estimated by applying the standard methods Sbet from the linear BET plots and F/ from adsorption at relative pressure p/po=0.975) [7]. The mesopore structure was characterized by the distribution function of mesopore volume calculated by the Barret-Joyner-Halenda (BJH) method [27]. In Table 2 the values of these parameters are given for both synthesized polymers. The melamine-formaldehyde resin MEA has a more developed pore structure (5 B 7=220mVg, F,=0.45cm /g) and narrower mesopores (D=7.3nm) in comparison to the phenolic-formaldehyde polymer PHD. 

Acetal, (Polyacetal) Poly-oxymethylene (POM) Acetal is a polymer obtained through an addition reaction of formaldehyde — (CH2—0) . It excels in mechanical performance and is regarded as a prominent engineering polymer. It appeared in 1959 with the commercial name Delrin . A short time later a useful copolymer was also developed with a cyclic ether like ethylene oxide. The monomer formaldehyde is a gas produced mostly by oxidizing methanol, and it is very useful in thermoset polymers like phenol, urea and melamine-formaldehydes. For high purity it is initially converted to trioxane or paraformaldehyde. The polymerization is carried out by ionic mechanism, wherein the monomer is dispersed in an inert liquid (heptane). The molecular weights reach 20,000 to 110,000. 

The first completely synthetic plastic material was made from the condensation of phenol and formaldehyde in the presence of a catalyst. The production of this material was perfected by Leo Hendrik Baekland (1863-1944), a Belgian chemist working in the United States, and it was marketed from 1909 under the name Bakelite. Bakelite is a highly crosslinked three-dimensional thermosetting polymer, and in the 1920s and 1930s a number of similar materials were developed such as urea formaldehyde and melamine formaldehyde. 

Melamine-formaldehyde acts as an amine when dissolved in dilute acid, usually HCl. During polymerization, between 20 and 80 monomeric units combine to form a polymer of colloidal dimensions (6-30 nm) with the elimination of water and HCl (56,57). The development of cationicity is associated with the loss of HCl, since a unit of charge on the polymer is generated for every mole of acid lost, and the pH decreases steadily during the polymerization. In a typical formulation at 12% solids at room temperature, polymerization is complete in about 3 h. The initially colorless solution develops a light blue haze and shows a strong Tyndall effect. 

Several copolymers and condensates of oxidized starches with polymers have been developed. For example, products of starch dialdehyde condensation with acrylamide were prepared for further copolymerization with various monomers to form resins for coatings, molding powders,585 and materials for immobilization of enzymes, for instance, alpha amylase.586 Hypochlorite-oxidized starches were also reacted with acrylonitrile.507,521 Hypochlorite-oxidized starches were allowed to react with allylated starch dialdehyde,587 polycondensates of ammonia-dimethylamine-epichlorohydrin,588 polycondensates of starch dialdehyde with melamine,589 urea433,541,590 capable of precipitation of tannin591, carboxyamides,411 urea and formaldehyde,592 proteins,524,593,594 polyfyinyl alcohol),595 alkylammonium salts,519,596 alkoxyalkylamines,597... 

Other polycondensation reactions which lead to finely dispersed polymers in liquid polyethers are the polycondensation reactions of urea and melamine with aqueous formaldehyde [92-95]. The reaction medium is usually polyether polyols, PO homopolymers or PO-EO copolymers (random or block copolymers), with MW of 3000-5000 daltons. During the polycondensation reaction, the aminoplast polymer precipitates, being insoluble in polyether and water (water from formaldehyde solution and reaction water), is eliminated by vacuum distillation. A variant of this reaction is to develop the polycondensation in water, and water containing the aminoplast polymer (as a viscous solution) is added to a polyether polyol, under vacuum, and at high temperature (100-130 °C), water being continuously eliminated from the reaction medium. The aminoplast insoluble polymer precipitates in the form of fine particles. 

Since sucrose might seem to be an ideal monomer in polymerization reactions, a very large variety of reactions of this type have been investigated in Sugar Research Foundation supported projects. In the 1940 s, ethylene oxide was combined with sucrose, but the products obtained did not lend themselves directly to commercial development. The first intensive efforts to produce polymers occurred concurrently with the sugar ester detergent activities in the 1950 s. These efforts included studies of the polymerization of sucrose with urea, vinyl acetate,phenol and formaldehyde, ammonia cuid hydrogen, melamine and formaldehyde and meuiy other variations. 

A patent review [4] showed that early intumescent formulations incorporated in polymers contained a precursor of phosphoric or polyphosphoric acid, a pentaerythritol type char source, and melamine, as typical formulations of intumescent coatings. Further developments tried to reduce the complexity of the additive system, for example by using a binary combination of the add precursor with nitrogen-containing compounds, which also act as a char source. While the add source is generally APP, typical examples of the second component are produds of condensation of formaldehyde with substituted ureas products of readions between aromatic diisocyanates and pentaerythritol or melamine polymers containing the piperazine ring in the main chain, also combined with substituted s-triazine, hydroxyalkyl isocyanurate etc. 

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