Urea-formaldehyde polymers resin preparation

When crosslinked, amino resins are very resistant to most organic solvents, though they tend to be attacked by both acids and alkalis. Urea-formaldehyde polymers are more susceptible to attack than those prepared from melamine and formaldehyde. 

Hexamethylolmelamine can further condense in the presence of an acid catalyst ether linkages can also form (see Urea Formaldehyde ). A wide variety of resins can be obtained by careful selection of pH, reaction temperature, reactant ratio, amino monomer, and extent of condensation. Liquid coating resins are prepared by reacting methanol or butanol with the initial methylolated products. These can be used to produce hard, solvent-resistant coatings by heating with a variety of hydroxy, carboxyl, and amide functional polymers to produce a cross-linked film. 

In the early 1930 s, a second type of resin prepared from formaldehyde was introduced to the market—namely, urea-formaldehyde resins. A few years later, melamine-formaldehyde resins also appeared. The same basic process is employed in polymerization of all these resins it consists of the catalyzed reaction of formaldehyde with the second ingredient—phenol, urea, or melamine—to evolve water and produce three-dimensional, cross-linked thermosetting polymers. 

Step-growth polymerization is a very important method for the preparation of some of the most important engineering and specialty polymers. Polymers such as polyamides [7], poly(ethylene terephthalate) [8], polycarbonates [9], polyurethanes [10], polysiloxanes [11], polyimides [12], phenol polymers and resins, urea, and melamine-formaldehyde polymers can be obtained by step-growth polymerization through different types of reactions such as esterification, polyamidation, formylation, substitution, and hydrolysis. A detailed list of reaction types is shown in Table 3.2. 

Formaldehyde is employed in the production of aminoplasts and phenoplasts, which are two different but related classes of thermoset polymers. Aminoplasts are products of the condensation reaction between either urea (urea-formaldehyde or UF resins) or melamine (melamine-formaldeliyde or MF resins) with formaldehyde. Phenoplasts or phenolic (phenol-formaldehyde or PF) resins are prepared from the condensation products of phenol or resorcinol and formaldehyde. 

Currently, the bulk of the conunercial polymers that would fit into this category are urea-formaldehyde and melamine-formaldehyde resins. Over the years, however, many other materials that might fit into this group were prepared but not adopted for use for various reasons. 

Urea-formaldehyde resin (UF) is a hydrophilic condensation polymer. The UF monosized non-porous microspheres were prepared with (-I-) L-2-amino-5-ureidopentanoic acid as the chiral ligand. The micro-spheres exhibited exceptional mechanical strength, chemical stability in the pH range 1-13, and low tendency toward swelling in solvents they were used for the CLEC separation of amino acids. Later, the porous UF microspheres were also prepared and L-proline was grafted via epichlorohydrin onto the polymer (l-proline content 0.28 mmol/g). Eighteen D,L-amino acids were resolved on the sorbent with aqueous ammonia... 

Alkanolamines are used as cross-linking and hardener accelerators in epoxy resins applications. Improved thermal and oxidative stability of polyvinyl alcohol, poly(phenylene ether), polystyrene, polypropylene, and polyethylene polymers are achieved by the addition of small amounts of the alkanolamines. Diethanolamine and morpholine act as initiators for the preparation of poly (alkyl methacrylate) in bulk or solution polymerization. The ethanolamines are efficient initiators for the preparation of polyvinyl chloride. Alkanolamines promote cross-linking of styrene copolymers with polystyrene or polyvinyl alcohol. Addition of alkanolamines to phenolic formaldehyde or urea formaldehyde resins affords improved electrical properties and increased water solubility. 

The cyclic diether, 1,3-dioxolane, is recommended by Ferro Corporation as a more benign solvent substitute for chlorinated organic solvents, such as methylene chloride, 1,2-dichloroethane, and 1,1,1-trichloroethane, and for ketones, such as methyl ethyl ketone (MEK). This ethylene glycol-based ether is a suitable solvent under neutral and basic conditions in several major-use areas. It is a powerful solvent for softening and dissolving polymers made from polar monomers, for example, polycarbonates, acrylates, cellulosics urethanes, phenoUcs, nitriles, urea-formaldehydes, and alkyds, as well as polyesters, vinyl epoxys, and halogen-containing polymers. As a reaction solvent it is added as a component to a special quaternary ammonium or phosphonium salt solution for preparation of a vesicular phenoxy resin. Other beneficial uses for the solvent dioxolane, include ... 

Urea-formaldehyde resin (UF) is a hydrophilic condensation polymer. The UF monosized nonporous microspheres were prepared with (-i-) L-2-amino-5-ureido-... 

In a number of cases, PAMAM dendrons were also prepared on other polymer particle cores, such as alumina, chitosan, cellulose, zirconia-urea-formaldehyde resin, silica-coated magnetite, and carbon nanotubes. Like the silica support (see above), at least in the case of the chitosan, the theoretically predicted propagation of the dendrons was not achieved, presumably due to the steric hindrance in the support pores. 

Formaldehyde-based resins were the first network polymers prepared by step polymerization to be successfully commercialized. They are prepared in two stages. The first involves the formation of a prepolymer of low molar mass which may either be liquid or solid. In the second stage the prepolymer is forced to flow under pressure to fill a heated mould in which further reaction takes place to yield a highly crosslinked, rigid polymer in the shape of the mould. Since formaldehyde is difunctional, the coreactants must have a functionality, /, eater than two and those most commonly employed are phenol (/= 3), urea (/= 4) and melamine (/= 6)... 

Amino resins are condensation thermosetting polymers of formaldehyde with either urea or melamine. Melamine is a condensation product of three urea molecules. It is also prepared from cyanamide at high pressures and temperatures ... 

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. 

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... 

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