4-Diphenylmethane carbamate

In -this paper, we will shortly discuss our approach to prepare hydroxy-terminated MDl/BDO-based urethane oligomers and their 4-diphenylmethane carbamates, 18 and describe in more detail the synthesis of monodisperse hydroxy-terminated oligo(oxy-tetramethylenes), their use for the investigation of the prepolymer formation, and the synthesis of linear PU-elastomers with narrow (monodisperse) soft and/or hard segment length distribution by using the hydroxy-terminated segment precursors. The chemical structures of the model systems studied in this... 

From the hydrolysis of a polyether-based PU a diamine (or a polyamine) such as toluene diamine or diphenylmethane diamine, a polyol and carbon dioxide are formed. The resulting diamines are the precursors used for the synthesis of isocyanates [11,12,16,18]. The resulting polyol is the polyether polyol used for the initial synthesis of PU. Carbon dioxide results from the decomposition of the very unstable carbamic acid formed by the hydrolysis (20.2) ... 

The phosgene toxicity, separation of hydrochloric acid from excess phosgene, and the use of chlorinated solvents as a reaction medium are the major drawbacks of this reaction process. Extensive studies have suggested that carbamate and dicarbamate can serve as environmentally benign precursors for the synthesis of isocyanate and diisocyanate (1-5). Figure 1 illustrates nonphosgene routes for the synthesis of two important diisocyanates [i.e., 4,4 -diphenylmethane diisocyanate (MDI) and toluene diisocyanate(TDI)] via carbonate and carbamate. 

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. 

A slurry of 550 g. ethyl N-hydroxy-carbamate potassium salt, 642 g. bromo-diphenylmethane, and NaHCOg in di-methylformamide stirred vigorously at 60° during 1.5-2 hrs. until neutral to moist litmus -> 178 g. ethyl N-benz-hydryloxycarbamate. 

Only the diisocyanates are of interest for urethane polymer manufacture and relatively few of these are employed commercially. The most important ones used in elastomer manufacture are the 2,4- and 2,6-toluene diisocyanates (TDl) 4,4 -diphenylmethane diisocyanates (MDI) and its aliphatic analogue 4,4 -dicyclohexylmethane diisocyanate (Hi2 MDI) 1,5-naphthalene diisocyanate (NDI) 1,6-hexamethylenediisocyanate (HDI) xylyene diisocyanate (XDI), isophorone diisocyanate (IPDI) and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (TMDI). Also manufactured commercially are various monoisocyanates, including methyl, /7-propyl, /7-butyl, cyclohexyl, phenyl, and 4-chloro- and 3,4-dichlorophenyl isocyanates which are used for substituted ureas and carbamates important as herbicides and crop protection agents. 

Fig. 13. IR spectra of the diphenylmethane-4-carbamate of a-hydro-o)-hydroxydodeca (oxytetramethylene), POTM-1 2-Urethane, in the NH (Fig. 13a) and carbonyl region (Fig. 13b) after different thermal treatment as indicated (temperatures of spectra recording - if not room temperature - given in parentheses).

Laser flash photolysis of model compounds of diphenylmethane-4,4 -diisocyanate based polyurethane low molecular weight model compounds, such as mono- and bis-carbamates, exhibits the formation of diarylmethyl radicals which readily react with oxygen. The formed polymer peroxy (PO2) radicals abstract hydrogen and yield polymer hydroperoxides (POOH) [1000, 1001, 1003, 1006, 1007]. 

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