Condensation polymers formaldehyde resins

The resin most often used with DNQ resists is the reddish-colored novolac (cresol-formaldehyde condensation polymers). The resins adhere well to most metal surfaces and form good films. Additionally, they are soluble in alkaline solutions and many common solvents, and they are capable of coupling with the DNQ sensitizer. The structure of novolac (X) is shown below. °... 

The reaction conditions can be varied so that only one of those monomers is formed. 1-Hydroxy-methylurea and l,3-bis(hydroxymethyl)urea condense in the presence of an acid catalyst to produce urea formaldehyde resins. A wide variety of resins can be obtained by careful selection of the pH, reaction temperature, reactant ratio, amino monomer, and degree of polymerization. If the reaction is carried far enough, an infusible polymer network is produced. 

A series of compounded flame retardants, based on finely divided insoluble ammonium polyphosphate together with char-forming nitrogenous resins, has been developed for thermoplastics (52—58). These compounds are particularly useful as iatumescent flame-retardant additives for polyolefins, ethylene—vinyl acetate, and urethane elastomers (qv). The char-forming resin can be, for example, an ethyleneurea—formaldehyde condensation polymer, a hydroxyethylisocyanurate, or a piperazine—triazine resin. 

Aniline—formaldehyde resins were once quite important because of their excellent electrical properties, but their markets have been taken over by newer thermoplastic materials. Nevertheless, some aniline resins are stiU. used as modifiers for other resins. Acrylamide (qv) occupies a unique position in the amino resins field since it not only contains a formaldehyde reactive site, but also a polymerizable double bond. Thus it forms a bridge between the formaldehyde condensation polymers and the versatile vinyl polymers and copolymers. 

Platinum-group metals (qv) form complexes with chelating polymers with various 8-mercaptoquinoline [491-33-8] derivatives (83) (see Chelating agents). Hydroxy-substituted quinolines have been incorporated in phenol—formaldehyde resins (84). Stannic chloride catalyzes the condensation of bis(chloromethyl)benzene with quinoline (85). 

Most processors of fiber-reinforced composites choose a phenol formaldehyde (phenoHc) resin because these resins are inherently fire retardant, are highly heat resistant, and are very low in cost. When exposed to flames they give off very Htde smoke and that smoke is of low immediate toxicity. PhenoHc resins (qv) are often not chosen, however, because the resole types have limited shelf stabiHty, both resole and novolac types release volatiles during their condensation cure, formaldehyde [50-00-0] emissions are possible during both handling and cure, and the polymers formed are brittle compared with other thermosetting resins. 

Though less prevalent than addition polymerization, condensation polymerization produces important polymers such as polyesters, polyamides (nylons), polycarbonates, polyurethanes, and phenol-formaldehyde resins (Chapter 12). 

Phenol-formaldehyde resins are the oldest thermosetting polymers. They are produced by a condensation reaction between phenol and formaldehyde. Although many attempts were made to use the product and control the conditions for the acid-catalyzed reaction described by Bayer in 1872, there was no commercial production of the resin until the exhaustive work by Baekeland was published in 1909. In this paper, he describes the product as far superior to amber for pipe stem and similar articles, less flexible but more durable than celluloid, odorless, and fire-resistant. ° The reaction between phenol and formaldehyde is either base or acid catalyzed, and the polymers are termed resols (for the base catalyzed) and novalacs (for the acid catalyzed). 

The workhorse of the VLSI industry today is a composite novolac-diazonaphthoquinone photoresist that evolved from similar materials developed for the manufacture of photoplates used in the printing industry in the early 1900 s (23). The novolac matrix resin is a condensation polymer of a substituted phenol and formaldehyde that is rendered insoluble in aqueous base through addition of 10-20 wt% of a diazonaphthoquinone photoactive dissolution inhibitor (PAC). Upon irradiation, the PAC undergoes a Wolff rearrangement followed by hydrolysis to afford a base-soluble indene carboxylic acid. This reaction renders the exposed regions of the composite films soluble in aqueous base, and allows image formation. A schematic representation of the chemistry of this solution inhibition resist is shown in Figure 6. 

Baekeland recognized that the trifunctional phenol would produce network polymers and therefore used difunctional ortho- or para-substituted phenols to produce linear paint resins. Linear thermoplastic products are formed by alkaline or acid condensation of formaldehyde with phenol derivatives such as /r-cresol (structure 4.81). 

Urea and melamine are tetra- and hexa-functional molecules. However, the formation of a network polymer is prevented by adding alcohols such as w-butanol and by condensing with formaldehyde at low temperatures under basic conditions. While phenol resins have better moisture and weather resistance than urea resins, the latter are preferred for light-colored... 

In far too many instances trade-name polymer nomenclature conveys very little meaning regarding the structure of a polymer. Many condensation polymers, in fact, seem not to have names. Thus the polymer obtained by the step polymerization of formaldehyde and phenol is variously referred to a phenol-formaldehyde polymer, phenol-formaldehyde resin, phenolic, phenolic resin, and phenoplast. Polymers of formaldehyde or other aldehydes with urea or melamine are generally referred to as amino resins or aminoplasts without any more specific names. It is often extremely difficult to determine which aldehyde and which amino monomers have been used to synthesize a particular polymer being referred to as an amino resin. More specific nomenclature, if it can be called that, is afforded by indicating the two reactants as in names such as urea-formaldehyde resin or melamine-formaldehyde resin. 

The high-molecular-weight products formed by the condensation of phenols with carbonyl compounds (especially with formaldehyde) are known as phenolic resins. They are mixtures of structurally nonuniform compounds that are initially soluble and fusible but which can become crosslinked (cured) by subsequent reactions. One distinguishes between acid- and base-catalyzed condensations, since they lead to different end products the properties of the condensation polymer are also affected by the mole ratio of phenol to formaldehyde. 

Chen (29) found that the amount of sulfuric acid directly determines the hardening time in the acid condensation of spent sulfite liquors used in plywood and veneers. However, in general the adhesives based purely on acid condensed lignins have often been found to be an uneconomic and qualitatively inferior alternative to adhesives based on synthetic polymers and phenol or lignin-formaldehyde resins. 

The first synthetic plastics were the phenol-formaldehyde resins introduced by Baekeland in 1907 [1], Melamine and urea also react with formaldehyde to form intermediate methylol compounds which condense to cross-linked polymers much like phenol-formaldehyde resins. Paper, cotton fabric, wood flour or other forms of cellulose have long been used to reinforce these methylol-functional polymers. Methylol groups react with hydroxyl groups of cellulose to form stable ether linkages to bond filler to polymers. Cellulose is so compatible with these resins that no one thought of an interface between them, and the term reinforced composites was not even used to describe these reinforced systems. 

Melamine, a white powder, was discovered and identified by Liebig in 1834 but commercial manufacture came only in 1939, by Cyanamid Company of America with dicyandiamide as raw material. Melamine is 2,4,6-triamino-l,3,5-triazine with a structure as shown in Figure 53. On reaction with formaldehyde in aqueous solution the melamine powder dissolves rapidly on heating to form various methylol melamines, as in Figure 54. After further heating and the elimination of water the methylol melamines condense to form resinous polymers. 

The broadest classification for plastics is the old thermoplastic and thermosetting . Examples of the former group are polyethylene, polystyrene, and poly-(methyl methacrylate) examples of the latter are urea-formaldehyde condensation polymers, powder coatings based on polyesters, epoxy resins, and vulcanized synthetic elastomers. 

Plywood and particle board are often glued with cheap, waterproof urea-formaldehyde resins. Two to three moles of formaldehyde are mixed with one mole of urea and a little ammonia as a basic catalyst. The reaction is allowed to proceed until the mixture becomes sympy, then it is applied to the wood surface. The wood surfaces are held together under heat and pressure, while polymerization continues and cross-linking takes place. Propose a mechanism for the base-catalyzed condensation of urea with formaldehyde to give a linear polymer, then show how further condensation leads to cross-linking. (Hint The carbonyl group lends acidity to the N—H protons of urea. A first condensation with formaldehyde leads to an inline, which is weakly electrophilic and reacts with another deprotonated urea.)... 

While catalysts are also used in the production of other types of polymers, the properties of most of these materials are not particularly dependent on the type of catalyst employed. Many poly condensation reactions, e. g. the formation of polyesters, polyamides or urea-formaldehyde resins, are speeded up by addition of some Bronsted or Lewis acids. Since relevant properties of these polymer products, such as their average chain lengths, are controlled by equilibrium parameters, primarily by the reaction temperatures and molar ratios of the monomers employed, and since their linkage patterns are dictated by the functional groups involved, addition of a catalyst has little leverage on the properties of the resulting polymer materials. 

The phosphorylation of phenol-furfural condensate affords a cation-exchange resin with improved thermal and chemical reristance. The heat treatment of phosphonic add resins from furfural redns, phenol-resorcinol-formaldehyde resin, and polystyrene at 100-180 °C for 10-48 h shows that the furfural-based phosphonic acid resins possess higher thermal stability than those from the other two polymers. 

A condensation polymer is one in which the repeating unit lacks certain atoms which were present in the monomer(s) from which the polymer was formed or to which it can be degraded by chemical means. Condensation polymers are formed from bi- or polyfunctional monomers by reactions which involve elimination of some smaller molecule. Polyesters (e.g., 1-5) and polyamides like 1-6 are examples of such thermoplastic polymers. Phenol-formaldehyde resins (Fig. 5-1) are thermosetting condensation polymers. All these polymers are directly synthesized by condensation reactions. Other condensation polymers like cellulose (1-11) or starches can be hydrolyzed to glucose units. Their chemical structure indicates that their repealing units consist of linked glucose entities which lack the elements of water. They are also considered to be condensation polymers although they have not been synthesized yet in the laboratory. 

Carbonaceous materials (CMs) are sometimes also named polymeric carbons. They are mostly prepared by thermal decomposition of organic precursors. One strategy is pyrolysis of gaseous or vaporized hydrocarbons at the surface of heated substrates, a second is heating (pyrolysis) of natural or synthetic polymers, both in an inert atmosphere. The latter is of special interest, and according to Miyabayashi et al. [374], precursors such as condensed polycyclic hydrocarbons, polymeric heterocyclic compounds, phenol-formaldehyde resins, polyacrylonitrile or polyphenylene are heated to 300-3000 °C for 0.15-20 h. Sometimes, a temperature/time profile is run. The temperature range must be divided into two domains, namely... 

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