Isocyanurate-urethanes

Owens-Corning claimed the use of ammonium fluoroborate or potassium fluoroborate as smoke suppressant in isocyanurate-urethane.107 It was believed that the fluoroborate decomposition products such as BF3, KF, or NH4F act as free radical chain stopper and add across double bounds of olefinic decomposition products. NASA reported that both ammonium fluoroborate and potassium fluoroborate are the effective endothermic fillers of ablative intumescent coating.108... 

Frisch, Patel, and Marsh [28] also reported on the preparation of isocyanurate-urethane foams and briefly reviewed the early developments in the field of polyisocyanurates. 

Catalysis is usually accompHshed through the use of tertiary amines such as triethylenediamine. Other catalysts such as 2,4,6-/m(/V,/V-dimethylaminomethyl)phenol are used in the presence of high levels of cmde MDI to promote trimerization of the isocyanate and thus form isocyanurate ring stmctures. These groups are more thermally stable than the urethane stmcture and hence are desirable for improved flammabiUty resistance (236). Some urethane content is desirable for improved physical properties such as abrasion resistance. 

Urethane network polymers are also formed by trimerization of part of the isocyanate groups. This approach is used in the formation of rigid polyurethane-modified isocyanurate (PUIR) foams (3). 

The formation of isocyanurates in the presence of polyols occurs via intermediate aHophanate formation, ie, the urethane group acts as a cocatalyst in the trimerization reaction. By combining cyclotrimerization with polyurethane formation, processibiUty is improved, and the friabiUty of the derived... 

Modification of cellular polymers by incorporating amide, imide, oxa2ohdinone, or carbodiimide groups has been attempted but only the urethane-modified isocyanurate foams are produced in the 1990s. PUIR foams often do not require added fire retardants to meet most regulatory requirements (34). A typical PUIR foam formulation is shown in Table 6. 

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

The isocyanurate reaction occurs when three equivalents of isocyanate react to form a six-membered ring, as shown in the fifth item of Fig. 1. Isocyanurate linkages are usually more stable than urethane linkages. Model compound studies show no degradation of the trimer of phenyl isocyanate below 270°C [10,11]. Catalysts are usually needed to form the isocyanurate bond. Alkali metals of carboxylic acids, such as potassium acetate, various quaternary ammonium salts, and even potassium or sodium hydroxide, are most commonly used as catalysts for the isocyanurate reaction. However, many others will work as well [12]. 

The isocyanurate reaction can be both beneficial and troublesome. It can be the bane of production engineers. Low levels of alkaline impurities present in urethane raw materials such as polyols, tackifiers, etc., can cause problems in prepolymer production, resulting in high viscosity products at levels of 5 ppm or less. At higher levels of alkaline impurities, more serious problems can occur, including poor shelf life, poor caulkability, or poor sag resistance. At levels of 15 ppm or higher, the alkalinity can cause an isocyanurate reaction in a prepolymer that can result in a gelled reactor. 

A cellular plastic - usually of the urethane or isocyanurate families - where chemical components are mixed at the spray head. 

The volatility of difunctional isocyanates (such as tolylene diisocyanates, hexamethylene diisocyanate, etc.) creates many environmental problems in the urethane industry. These difficulties can be overcome by preparation of NCO-terminated oligomers with low vapor pressure. One approach is the preparation of NCO-ter-minated oligomers by partial cyclotrimerization of difunctional isocyanates. Usually this is achieved by a multi-step process which includes also deactivation of the catalyst at a certain conversion. During our work on cyclotrimerization of isocyanates we found that cyclic sulfonium zwitterions are very active cyclotrimerization catalysts (2). Recently we found that cyclic sulfonium zwitterions under certain reaction conditions act as anionic initiators. This behavior of cyclic sulfonium zwitterions permits preparation of isocyanate oligomers containing isocyanurate rings by a one-step procedure, eliminating the deactivation step. 

Figure 9.7. Comparison between IR spectra of Z1031-I (upper) and Z1030/1073 (lower) coatings (a) carbonyl of urethane groups (b) carbonyl of isocyanurate ring and urethane by-products (c) NH urethane and urethane by-products (d) CH2, CH3 (e) CFo, COC, backbone (f) isocyanurate ring (g) carbonyl of ureas and urethane by-products).

URETHANE POLYMERS] (Vol 24) PUIR foams. See Polyurethane-modified isocyanurate. 

The isocyanate (2270 cm"1) uretedinedione ring carbonyl (1780 cm"1) and urea carbonyl (1660 cm"1) groups can usually be identified. Carbonyls from ester, urethane, allophanate, isocyanuric acid ring and Biuret groups all absorb near 1730 cm 1 and are difficult to distinguish. Hydrogen bonds which can function as physical crosslinks in PU have been... 

A series of compounded flame retardants, based on finally divided insoluble ammonium phosphate together with char-forming nitrogenous resins, has been developed for thermoplastics.23 These compounds are particularly useful as intumescent flame-retardant additives for polyolefins, ethylene-vinyl acetate, and urethane elastomers. The char-forming resin can be, for example, an ethyle-neurea-formaldehyde condensation polymer, a hydroxyethyl isocyanurate, or a piperazine-triazine resin. Commercial leach-resistant flame-retardant treatments for wood have also been developed based on a reaction product of phosphoric acid with urea-formaldehyde and dicyandiamide resins. 

With regard to reactive flame-retardants, two routes can be followed to improve thermal stability and fire behavior of PU foams use of brominated or phosphorus-containing polyol or, for rigid foams, the introduction inside polymer backbone of more thermally stable structure than urethane, mainly isocyanurate, but also uretidione rings or carbodiimide.19... 

Three isocyanate groups can react to form a trimer or substituted isocyanurate ring. Phosphines or bases such as sodium acetate or sodium formate can catalyze this reaction. The isocyanurate ring is thermally stable, has good chemical resistance, and can enhance the resistance of a urethane adhesive to aggressive environments. 

The polyisocyanates which can be used for preparing isocyanate-based foams are mainly aromatic compounds and some aliphatic or aralkyl polyisocyanates. TDI (toluene diisocyanate) is widely used for flexible foams. Pure MDI (diphenylmethane diisocyanate) is used for elastomers and coatings. Modified TDI and modified MDI are used for high-resilience flexible foams. Polymeric isocyanates (polymeric MDI or oligomeric MDI) are mostly used for preparing rigid urethane and isocyanurate foams, and in part, for preparing flexible and semi-flexible foams. 

Modification of poly(carbodiimide) foams with polyols afford hybride foams containing urethane sections. However, the thermal stabilities of the poly (urethane carbodiimide) foams are lower. Using isocyanate trimerization catalysts, such as l,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine, in combination with the phospholene oxide catalyst gives poly(isocyanurate carbodiimide) foams with improved high temperature properties. The cellular poly(carbodiimide) foams derived from PMDI incorporate six-membered ring structures in their network polymer structure. ... 

There are a few other chemical reactions on the wood surface that could make important contributions. One is that of moisture on the surface of wood to form an unstable carbamic acid group that quickly decomposes to form a primary amine with evolution of carbon dioxide. The primary amine formed has active hydrogens reactive to isocyanate. Other successive reactions ensue leading first to disub-stituted ureas and then to biurets. Furthermore, isocyanate reaction with urethane to form allophanates, and trimerization of isocyanates to form isocyanurate are also possible to variable extents, under the conditions of bonding. The different reactions are summarized in Scheme 2. 

In addition to these unmodified foams, many modified or hybrid foams have appeared in the literature, e.g., urethane-modified isocyanurate foams, isocyanurate-modified urethane foams, urea-modified isocyanurate foams, unsaturated poIyester-poI)rurethane hybrid foams, etc. 

Modified polyisocyanates are prepared by incorporating at least one linkage into monomeric polyisocyanates. Such linkages include urethane, carbodiimide, allophanate, biuret, amide, imide, isocyanurate, and oxazolidone. These modifications provide some advantages, e.g., lower vapor pressure, increased viscosity, and controlled reactivity. 

Some examples of modified polyisocyanates are isocyanate-terminated quasi-prepolymers (semi-prepolymers), urethane-modified MDI, carbodiimide-modified MDI, isocyanurate-modified TDI, and isocyanurate-modified isophorone diisocyanate. 

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