Polyesterification reactions

The oxidation reactor effluent and methanol ate sent to the esterification reactor, which operates at up to 250°C and a pressure sufficient to maintain the Hquid phase. This latter is about 2500 kPa (25 atm). The oxidation products are converted to methyl -toluate and dimethyl terephthalate without a catalyst. Excess methanol is suppHed, and steam and vaporized methanol ate removed and enter a methanol recovery column. The esterification products flow to a cmde ester column, which separates the toluate from the terephthalate. The overhead stream of methyl -toluate is returned to the oxidation reactor, and the bottoms stream of dimethyl terephthalate goes to a primary distillation. The distillate is dissolved in methanol, crystallized, and sohd dimethyl terephthalate is recovered. The dimethyl terephthalate can then be either recrystallized or distilled to yield the highly pure material needed for the polyesterification reaction. 

The polyesterification reaction is normally carried out in stainless steel vessels ranging from 8,000—20,000 L, heated and cooled through internal cods (Fig. 1). Blade agitators revolving at 70—200 rpm ate effective in stirring the low viscosity mobde reactants, which ate maintained under an inert atmosphere of nitrogen or carbon dioxide during the reaction at temperatures up to 240°C. 

Table 6. Gel Points of Polyesterification Reaction Systems with Stoichiometric Reactants ...

An inert atmosphere is required in all cases and a vacuum line is often used for the removed of water at the end of the polyesterification reaction. 

Table 3. Kinetic parameters of esterification and polyesterification reactions. - The listed values relate to the following cases Reactions where at least one of the two reactants is difunctional and reactions between two monofunctional reactants having more than 4 carbon atoms in their molecule. Table is in two parts Part 1 (page 99 to 122) for experimental conditions. Part 2 (page 122 to 142) for results and references. 

Within the wide range of phosphorus compounds described as activating agents for polyesterification reactions,2,310 triphenylphosphine dichloride and diphenylchlorophosphate (DPCP) were found to be the most effective and convenient ones. In pyridine solution, DPCP forms a A-phosphonium salt which reacts with the carboxylic acid giving the activated acyloxy A -phosphonium salt. A favorable effect of LiBr on reaction rate and molar masses has been reported and assumed to originate from the formation of a complex with the A-phosphonium salt. This decreases the electron density of the phosphorus atom... 

Sulfur compounds have also been widely studied as activating agents for polyesterification reactions. p-Toluenesulfonyl chloride (tosyl chloride) reacts with DMF in pyridine to form a Vilsmeir adduct which easily reacts with carboxylic acids at 100-120° C, giving highly reactive mixed carboxylic-sulfonic anhydrides.312 The reaction is efficient both for aromatic dicarboxylic acid-bisphenol312 and hydroxybenzoic acid314 polyesterifications (Scheme 2.31). The formation of phenyl tosylates as significant side products of this reaction has been reported.315... 

Unsaturated polyesters were obtained by reacting the glycolyzed product widi maleic anhydride at a hydroxy-to-carboxyl ratio of 1 1. The hydroxyl number was determined without separation of die free glycol. The polyesterification reaction was conducted in a 2-L round-bottom dask equipped with a condenser, a gas bubbler, a thermowell, and a stirrer. The reaction mixture was heated from room temperature to 180°C in about 1-1.5 h. The temperature was maintained at 180°C for about 3 h, dien raised to 200°C and maintained until die acid value reached 32 mg KOH/g. 

In the polyesterification process p is directly calculated from the carboxyl group titer. Results for the polyesterification reaction between diethylene glycol and adipic acid at 166° and 202°C are plotted in Fig. 3 in accordance with the third-order equation (8). For comparison purposes, the course of the non-polymer-forming reaction of diethylene glycol with the monobasic acid, caproic, is also shown. Eq. (8) is not obeyed from zero to 80 percent esterification [l/(l—p) =l to 25], as is shown by the curvature over this region. From 80 to 93 percent esterification the reaction appears to be third order. The non-polymerforming esterification of diethylene glycol with caproic acid (and other... 

A common characteristic to all the chemical reactions involved in step polymerisation that should be emphasised is that they are most often equilibrated reactions. For instance, the polyesterification reaction is based on the esterification/hydrolysis equilibrium... 

The kinetics of polycondensation reactions might be expected to be similar to those found in condensation reactions of small molecules (evidence suggests that rate coefficients are independent of polymer size). Polyesterification reactions between dibasic carboxylic acids and glycols can be catalysed by strong acids. In the absence of added catalyst, it has been suggested that the acidic monomer should act as a catalyst, whereupon the rate of reaction should be given by... 

Consider the condensation polyesterification reaction between ethylene glycol, H0-(CH2)2-0H, and terephthalic acid, HOOC-Ph-COOH, each of which has an initial concentration of 1.0 mol/liter. Calculate the number average and weight average degrees of polymerization at 1, 5, and 20 hours. The forward reaction rate constant for the polymerization reaction is 10.0 liter/mol hr, and second-order, catalyzed kinetics can be assumed. 

Tartaric acid-glycerol polyesters were reported in 1847 by Berzelius [13] and those of ethylene glycol and succinic acid were reported by Lorenzo in 1863 [14]. Carothers and Van Natta [15] extended much of the earlier work and helped clarify the understanding of the polyesterification reaction in light of the knowledge of polymer chemistry at their time. Polyethylene terephthalate [16, 17] and the polyadipates [18] (for polyurethane resins) were the first major commercial application of polyesters. 

The polyesterification reaction is reversible because it is influenced by the presence of condensate water in equilibrium with the reactants and the polymer. The removal of water in the latter part of the reaction process is essential for the development of optimum molecular weight, on which the ultimate structural performance depends. 

The polyesterification reaction is carried out in the presence of an inert gas, such as nitrogen or carbon dioxide, to prevent discoloration. Usually, the sparge rate of the inert gas is increased in the final stages of polyesterification to assist the removal of residual water. Although the removal of water can be facilitated by processing under vacuum, this is rarely used on a commercial scale. 

Much effort has been devoted to the optimization of the polyesterification reaction. For instance, different types of monomeric precursors structurally related to succinic acid (e.g., dimethyl succinate or succinic anhydride) were used. Different kinds of catalysts (e.g., phenolates, titanium alkoxides, tin octanoates) at different concentrations were studied. Different reaction temperatures (130-190 °C) were reached and different procedures for water elimination (vacuum drying under different conditions or toluene distillation) were adopted. Experimental results obtained showed that the use of different catalysts and different monomer precursors (succinic acid derivatives) did not significantly alter the polymerization kinetics or yield, and for this reason, they were abandoned. The procedure finally adopted is summarized below. 

In this chapter we want to better understand how monomers react together to form long polymer chains. We have already seen a few reactions of organic compounds. For example, in Chapter 4 we wrote an equation for the esterification reaction of an alcohol with a carboxylic add to produce an ester plus water (Equation 5). We pointed out that monomers are usually difunctional organic compounds, where reaction with other suitable difunctional compounds can lead to polymer formation. In Chapter 4 we illustrated this with a polyesterification reaction (Equation 6). We will see that there are several different types of monomers. After reading this chapter you should be able to identify those organic compounds that are monomers and understand how they can react to form polymers. 

Measurements of dielectric properties have been used to monitor chemical reactions in organic materials for more than fifty years. In 1934, Kienle and Race 11 reported the use of dielectric measurements to study polyesterification reactions. Remarkably, many of the major issues that are the subject of this review were identified in that early paper the fact that ionic conductivity often dominates the observed dielectric properties the equivalence between the conductivity measured with both DC and AC methods the correlation between viscosity and conductivity early in cure the fact that conductivity does not show an abrupt change at gelation the possible contribution of orientable dipoles and sample heterogeneities to measured dielectric properties and the importance of electrode polarization at low frequencies. 

Solomon et al. [35] concluded that the observed high-order kinetics for esterification and polyesterification reactions ruled out unimolecular AacI AalI mechanisms, and that the Aac2 mechanism was the most likely. 

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