Isocyanate monomers, reaction

Organic isocyanates (R-N=C=0) are xenobiotics used extensively in the manufacture of paints, pesticides, and polyurethanes. The reactivity of the isocyanate group can also underlie the toxic reactions observed in patients that have been exposed to organic isocyanate monomers. Furthermore, the isocyanates formed in the body can be metabolites of various other xenobiotics, such as ... 

One alternative is to select precursors which form a gas as a reaction product in situ during the network formation of thermosets. However this approach is restricted to a very limited number of precursors reacting via a polycondensation mechanism to split off a gas. For example, flexible polyurethane foams are commercially produced using CO2 that is liberated as a reaction product of the isocyanate monomer with water [5]. Very recently, Macosko and coworkers studied the macroscopic cell opening mechanism in polyurethane foams and unraveled a microphase separation occurring in the cell walls. This leads to nanosized domains, which are considered as hard segments and responsible for a rise in modulus after the cell opening [6]. 

For those products laminated using reactive polyurethane based adhesives, suppliers have been aware for many years of the potential migration of amines formed by the reaction of unreacted isocyanate monomer with water and recommend that laminated products are given time to fully cure before they are used in contact with food. Adhesives have been developed that contain low levels of monomeric aromatic isocyanates, in order to reduce any potential migration of aromatic amines into food in critical applications. Such adhesives are not considered to present any notable amine migration hazard unless used in high-temperature applications. 

Sol in acet, tetrahydrofuran and eth acetate, si sol in n-heptane and methanol v si sol in toluene and w. Prepn of the initial polymer is from a dioxane soln at 50° of 2.0 equiv mol wts each of the monomers using either 1.5 equiv wt % of boron trifluoride etherate or 2.0 equiv wt % of vanadyl acetylacetonate as a catalyst to enhance the polymerization rate. Complete polymerization or gel is accomplished in about 70 hrs at 50°. The reaction rate is further enhanced by the addition of 0.072 equiv wt % of the isocyanate monomer after the initial reaction, resulting in gelation after 40 hrs at 50°. The hot dioxane soluble product is w pptd, vacuum steam-distd and dried. Post polymerization nitration of the polymer is accomplished with 100% nitric acid at 65°... 

Diisocyanates are an important class of chemicals of commercial interest, which are frequently used in the manufacture of indoor materials. such as adhesives, coatings, foams and rubbers (Ulrich, 1989). In some types of particle board, the diisocyanates have replaced formaldehyde. Isocyanates are characterized by the electrophilic -N=C=0 group, which can easily react with molecules containing hydroxy groups, such as water or alcohols. On hydrolysis with water, primary amines are formed, while a reaction with alcohols leads to carbamates (urethanes). Polyurethane (PUR) products are then obtained from a polyaddition of diisocyanate and diol components. Compounds commonly used in industrial surface technology are 4,4 -diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). The diisocyanate monomers are known as respiratory sensitizers and cause irritation of eyes, skin and mucous membrane. Therefore, polyisocyanates such as HDI-biuret and HDI-isocyanurate with a monomer content <0.5 % are used for industrial applications, and isocyanate monomers will not achieve high concentrations in ambient air. Nevertheless, it is desirable to measure even trace emissions from materials in private dwellings. 

The reactants for polyurethane flexible foams, of molecular weight <5000, are low viscosity liquids. CO2 gas is generated by the reaction of the 1-4% water content with the di-isocyanate monomer... 

Another type of polyol often used in the manufacture of flexible polyurethane foams contains a dispersed soHd phase of organic chemical particles (234—236). The continuous phase is one of the polyols described above for either slab or molded foam as required. The dispersed phase reacts in the polyol using an addition reaction with styrene and acrylonitrile monomers in one type or a coupling reaction with an amine such as hydrazine and isocyanate in another. The soHds content ranges from about 21% with either system to nearly 40% in the styrene—acrylonitrile system. The dispersed soHds confer increased load bearing and in the case of flexible molded foams also act as a ceU opener. 

For methylene diphenyl diisocyanate (MDI), the initial reaction involves the condensation of aniline [62-53-3] (21) with formaldehyde [50-00-0] to yield a mixture of oligomeric amines (22, where n = 1, 2, 3...). For toluene diisocyanate, amine monomers are prepared by the nitration (qv) of toluene [108-88-3] and subsequent hydrogenation (see Amines byreduction). These materials are converted to the isocyanate, in the majority of the commercial aromatic isocyanate phosgenation processes, using a two-step approach. 

The polyaddition reaction is influenced by the stmcture and functionaHty of the monomers, including the location of substituents in proximity to the reactive isocyanate group (steric hindrance) and the nature of the hydroxyl group (primary or secondary). Impurities also influence the reactivity of the system for example, acid impurities in PMDI require partial neutralization or larger amounts of the basic catalysts. The acidity in PMDI can be reduced by heat or epoxy treatment, which is best conducted in the plant. Addition of small amounts of carboxyHc acid chlorides lowers the reactivity of PMDI or stabilizes isocyanate terrninated prepolymers. 

The basic RIM process is illustrated in Fig. 4.47. A range of plastics lend themselves to the type of fast polymerisation reaction which is required in this process - polyesters, epoxies, nylons and vinyl monomers. However, by far the most commonly used material is polyurethane. The components A and B are an isocyanate and a polyol and these are kept circulating in their separate systems until an injection shot is required. At this point the two reactants are brought together in the mixing head and injected into the mould. 

Polyaddition reactions based on isocyanate-terminated poly(ethylene glycol)s and subsequent block copolymerization with styrene monomer were utilized for the impregnation of wood [54]. Hazer [55] prepared block copolymers containing poly(ethylene adipate) and po-ly(peroxy carbamate) by an addition of the respective isocyanate-terminated prepolymers to polyazoesters. By both bulk and solution polymerization and subsequent thermal polymerization in the presence of a vinyl monomer, multiblock copolymers could be formed. 

These conditions severely limit the range of initiators and monomers that can be used and require that attention to reaction conditions is of paramount importance. The relatively low incidence of side reactions associated with the use of azo-compounds (Section 3.3.1) has led to these initiators being favored for this application. Functional azo compounds used in telechelic syntheses include 9,19c> 198 10l99,2ml and ll20l,2<12. The acylazidc end groups formed with initiator 11 may be thermally transformed to isocyanate ends.201 2t, ... 

The synthesis of the oligomers involved the known reaction of isocyanates and cyanamide (Nl CN). For example, N-cyano-N -phenyl urea has been synthesized from phenyl isocyanate and an aqueous alkaline solution of cyanamide in high yield.(3) Recently, similar reactions were used to prepare various di-N-cyanourea compounds from diisocyanates. ( 1) These monomers were also synthesized directly by reacting diisocyanates with cyanamide at melt temperatures. 

Polyurethanes are useful in numerous applications such as reaction injection molding, rigid and flexible foams, coatings and adhesives. However, due to the high reactivity of the isocyanate group [96], yielding either dimers, via self-condensation or a carbamate via the reaction with an alcohol, the A,jB-monomers have to be produced in-situ in the reaction vessel. 

In this chapter we have examined the reactions and reactors used in polymerizing monomers. In many situations the production of monomers from feedstocks, the polymerization, and the forming of the polymer into products are done in the same chemical plant. In some cases the monomer is too reactive to be shipped to a polymerization plant (isocyanates, for example), and in some cases the producer does not want to be dependent on monomer suppliers. 

Japanese workers prepared examples of 2-alkenyl-4,5-oxazolediones 40a and 40b, which are key intermediates in the synthesis of alkenoyl isocyanates 41a and 41b (Scheme 6.13). These reactive monomers are precursors to a variety of functionalized polymers including instantaneously curable compositions. Thus, reaction of oxalyl chloride with acrylamide 39a or methacrylamide 39b affords 40a and 40b isolated as hydrochloride salts in high yields. Subsequent decomposition of the 2-alkenyl-4,5-oxazolediones in the presence of a metal halide or synthetic zeolite affords 41a and 41b contaminated with varying amounts of 42a and 42b. The synthesis and reactions of other 2-substituted 4,5-oxazolediones have been described independently by Speziale and co-workers ° and Sasaki and co-workers. ... 

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