Isocyanate reaction with hydroxyls

The catalyst selection for blocked isocyanates depends on the nature of the blocking agent, the desired cure temperature, the polyol structure, and the application. Mono-, di- and trialkyltin compounds are effective catalysts for many blocked isocyanate reactions with hydroxyl compounds. In most solvent-borne coatings, DBTDL is used as a catalyst. 

As often happens with polymerization reactions, simple rate laws can seldom describe the whole course of reaction because of catalysis or inhibition by the urethane groups formed or by the initial reagents. Self-association of metallic catalysts, or their loose complexation by products or reagents, also prevents correlation of rates of reaction by simple proportionality or even power-law relations. Catalysis of isocyanate reaction with hydroxyls [250, 251] is by far the best understood. 

Blocked isocyanate, for our purposes, will refer to the reaction product of a diisocyanate or isocyanate-terminated prepolymer in which the isocyanate functionality has been reacted with a blocking agent . Once blocked , the diisocyanate can be added to polyols or certain chain extenders, and these materials will not react at room temperature. The concept is shown in the sixth item of Fig. 1. An adhesive formulated with a blocked isocyanate is basically a two-component adhesive that does not react until heated to the activation temperature. When an adhesive is made with a blocked isocyanate together with hydroxyl-containing curatives, the adhesive has a good long shelf life at room temperature. However, once heated... 

Since the early days of polyurethane discovery, the technology has focused on isocyanate reactions with polyesters or polyethers. The differences will be discussed in later sections. These reactions are responsible for the growth of the polyurethane industry. The polyesters of interest to polyurethane chemists terminate in hydroxyl groups and are therefore polyols produced by the polycondensation of dicarboxyhc acids and polyols. An example is a polyol with a polycarbonate structure (Figure 2.3). 

Urethane adhesives take their name from the product of the most common step-growth polymerization reaction used to generate the adhesive polymers. Isocyanates react with hydroxyl groups to create urethane (or carbamate) linkages ... 

Isocyanates are very reactive toward compounds containing labile hydrogen atoms, forming addition compounds with the hydrogen donors. One such reaction, with hydroxyl-bearing compounds to form carbamates, or urethanes,... 

Figure 3.13 shows the reaction kinetics curves (conversion against time) of the phenyl isocyanate reaction with oligo-polyols having various percentages of primary hydroxyls. 

The carboxylic groups of mesoporphyrin-lX (15 b) and mesohemin-EX (15 c) were converted into isocyanate groups (15 d, c)66. The reaction with hydroxyl group containing crosslinked polymers like poly(2-hydroxyethylmethacrylate) or sephadex (with hydroxy-propyl groups) in pyridine at room temperature led to fixed porphyrins (20 a, b). 

Figure 6. Reactions of isocyanate (NCO) with hydroxyl to form urethane.

From this emphasis on hydroxyl groups, it might be thought that the hardening process consists solely of urethane formation between resin and polyisocyanate. This is obviously not so, since water vapour is usually present and the isocyanate reactions with water must proceed in competition with the reaction with hydroxyl. This will lead to consumption of isocyanate groups and linking of isocyanate molecules by urea linkages. With a difunctional isocyanate this tends to space the resin chains farther apart,... 

Isocyanates react with hydroxyl groups in a rearrangement reaction to form a urethane group. In the simple case, this can be described by an alcohol reacting with an isocyanate, as indicated below. 

These reactions are usually undesirable, since they lead to a decrease in the amount of isocyanate available for reaction with hydroxyl groups and produce carbon dioxide, which can cause bubbles in the polyurethane if it is formed late in the polymer s formation. 

Following this work, the y -12F-diol was used for the direct reaction with hexamethylene-1,6-diisocyanate in the presence of dibutyltin dilaurate to produce a cross-linked elastomer or a reactive prepolymer which was terminated with either isocyanate or hydroxyl groups, depending on which reactant was in excess (142,143). 

The hydroxyl number can be deterrnined in a number of ways such as acetylation, phthalation, reaction with phenyl isocyanate, and ir and nmr methods. An imidazole-catalyzed phthalation has been used to measure the hydroxyl number for a number of commercial polyether polyols and compared (favorably) to ASTM D2849 (uncatalyzed phthalation) (99). The uncatalyzed method requires two hours at 98°C compared to 15 minutes at the same temperature. 

Uretha.nes. Urethane elastomers are prepared by the reaction of an isocyanate molecule with a high molecular weight ester or ether molecule. The result is either an elastomeric mbber form or a Hquid prepolymer that can be vulcanised with an amine or a hydroxyl molecule (see Urethane POLYAffiRS). 

The most common catalyst used in urethane adhesives is a tin(lV) salt, dibutyltin dilaurate. Tin(IV) salts are known to catalyze degradation reactions at high temperatures [30J. Tin(II) salts, such as stannous octoate, are excellent urethane catalysts but can hydrolyze easily in the presence of water and deactivate. More recently, bismuth carboxylates, such as bismuth neodecanoate, have been found to be active urethane catalysts with good selectivity toward the hydroxyl/isocyanate reaction, as opposed to catalyzing the water/isocyanate reaction, which, in turn, could cause foaming in an adhesive bond line [31]. 

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