Melamine-formaldehydes development

Both melamine—formaldehyde (MF) and resorcinol—formaldehyde (RF) foUowed the eadier developments of phenol—, and urea—formaldehyde. Melamine has a more complex stmcture than urea and is also more expensive. Melamine-base resins requite heat to cure, produce colorless gluelines, and are much more water-resistant than urea resins but stiU are not quite waterproof. Because of melamine s similarity to urea, it is often used in fairly small amounts with urea to produce melamine—urea—formaldehyde (MUF) resins. Thus, the improved characteristics of melamine can be combined with the economy of urea to provide an improved adhesive at a moderate increase in cost. The improvement is roughly proportional to the amount of melamine used the range of addition may be from 5 to 35%, with 5—10% most common. 

Interesting developments were also taking place in the field of thermosetting resins. The melamine-formaldehyde materials appeared commercially in 1940 whilst soon afterwards in the United States the first contact resins were used. With these materials, the forerunners of today s polyester laminating resins, it was found possible to produce laminates without the need for application of external pressure. The first experiments in epoxide resins were also taking place during this period. 

In addition to the two basic groups of antifreeze admixtures, others containing superplastizisers such as sulfonated naphthalene formaldehyde (SNF) and sulfonated melamine formaldehyde (SMF) have been developed. The main advantage afforded by such admixtures is that they produce significant water-reduction. 

Urea—formaldehyde and melamine—formaldehyde reagents are resin formers, which not only cross-link cotton but also copolymerize with themselves. These have been used both as simple cross-linkers or prepolymer systems. If too much of the polymerization is concentrated on the fiber surface, the fabric may be sufficiendy stiffer that it takes on a boardy character. As such, the finisher must control the action of agent to give the desired crisp hand but prevent the development of boardiness. Melamines have been recommended for applications when complete shrink resistance is required. However, both finishes were rejected for the white-shirt market because of loss of strength when hypochlorite bleach is used on account of vulnerable NH groups and the ensuing discoloration (37). 

A recent innovation in in-situ microencapsulation is the development of acid-triggered release of pesticide from the microcapsules [12]. Diols and aldehydes are reacted to form an acid labile acetal moiety. The acetal is then reacted with isocyanate to create a prepolymer. The prepolymer is a polyisocyanate cmitaining the acid labile moiety and suitable for in-situ shellwall polymerization. The prepolymer is dissolved into a pesticide, emulsified into water, and shellwall formed in-situ. Under alkaline or neutral pH conditions in a container, the insecticide is safely contained in the microcapsules. Acid could be added to the spray tank to rapidly release capsule contents prior to application. Alternate shellwall chemistry for in-situ microencapsulation utilizes etherified urea-formaldehyde prepolymers in the oil phase that are self-condensed with acid catalyst to produce encapsulating aminoplast shellwalls [13]. This process does not have the problem of continuing CO2 evolution. Water-soluble urea-formaldehyde and melamine-formaldehyde prepolymers can be selected to microencapsulate water or aqueous solutions [14]. 

An overall trend towards an improvement of the properties of polymeric materials is also observed in the development of modified melamine-formaldehyde... 

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. 

Allergic dermatitis has been demonstrated from direct skin contact and from exposure to gaseous formaldehyde in the air. Various forms of reaction occur, from simple erythema to maculopapular lesions, hyperesthesia, and angioedema. Five patients developed an allergic contact dermatitis to plaster casts, caused by free formaldehyde released by a melamine-formaldehyde resin incorporated in the plaster. 

Materials from starch crosslinked with melamine-formaldehyde, methylated melamine-formaldehyde, and other amine-aldehyde resins were patented as binders for filter paper,1336 milk filter sheet materials,1338 and aqueous papercoating compositions containing clay, titanium(IV) oxide, butadiene-styrene latex, and calcium octadecanoate.1396,1397 Foams for filters were developed.1398 A heatsetting adhesive was one of the first applications reported for starch crosslinked by urea-formaldehyde and phenol-formaldehyde resins.1331,1340-1342,1347,1372,1399... 

CIBA had developed Cibanoid urea-formaldehyde, Cibanit aniline-formaldehyde, and melamine-formaldehyde resins. See Hans Stager, Modern organic materials at the Swiss National Exhibition Zurich, 1939, British Plastics and Moulded Products Trader, 11 (1939), 254-257. 

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. 

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