Homogeneous Polycondensations

Aromatic polycarbonates are currently manufactured either by the interfacial polycondensation of the sodium salt of diphenols such as bisphenol A with phosgene (Reaction 1, Scheme 22) or by transesterification of diphenyl carbonate (DPC) with diphenols in the presence of homogeneous catalysts (Reaction 2, Scheme 22). DPC is made by the oxidative carbonylation of dimethyl carbonate. If DPC can be made from cyclic carbonates by transesterification with solid catalysts, then an environmentally friendlier route to polycarbonates using C02 (instead of COCl2/CO) can be established. Transesterifications are catalyzed by a variety of materials K2C03, KOH, Mg-containing smectites, and oxides supported on silica (250). Recently, Ma et al. (251) reported the transesterification of dimethyl oxalate with phenol catalyzed by Sn-TS-1 samples calcined at various temperatures. The activity was related to the weak Lewis acidity of Sn-TS-1 (251). 

The effects of various reaction conditions are examined in detail, in which 1 mmol oftetramine (23) or (24) is reacted with 1 mmol ofdicarboxylic acid (15). As for the amount of solvent, 5 ml of PPMA is appropriate for the 1-mmol scale reaction. A higher concentration makes it difficult for the reaction to proceed homogeneously, whereas a lower concentration reduces the rate of reaction. The reduced viscosity markedly increases with increasing temperature, and the polycondensation of 15 and benzidine (23) at 140°C results in a sufficiently high reduced viscosity of 0.90 dl/g in 24 h. The reaction of 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane (15) with tetramines occurs slowly, requiring more than 24 h for completion, because (15) has the highly negative hexafluoroisopro-pylidene unit. 

Esterification is the first step in PET synthesis but also occurs during melt-phase polycondensation, SSP, and extrusion processes due to the significant formation of carboxyl end groups by polymer degradation. As an equilibrium reaction, esterification is always accompanied by the reverse reaction being hydrolysis. In industrial esterification reactors, esterification and transesterification proceed simultaneously, and thus a complex reaction scheme with parallel and serial equilibrium reactions has to be considered. In addition, the esterification process involves three phases, i.e. solid TPA, a homogeneous liquid phase and the gas phase. The respective phase equilibria will be discussed below in Section 3.1. 

Transesterification is the main reaction of PET polycondensation in both the melt phase and the solid state. It is the dominant reaction in the second and subsequent stages of PET production, but also occurs to a significant extent during esterification. As mentioned above, polycondensation is an equilibrium reaction and the reverse reaction is glycolysis. The temperature-dependent equilibrium constant of transesterification has already been discussed in Section 2.1. The polycondensation process in the melt phase involves a gas phase and a homogeneous liquid phase, while the SSP process involves a gas phase and two solid phases. The respective phase equilibria, which have to be considered for process modelling, will be discussed below in Section 3.1. 

According to the principles of polycondensation, all of the above reactions will also take place during SSP. The conditions for the latter, however, are different as this process is carried out at lower temperatures in a non-homogeneous environment. In order to examine the kinetics of SSP, some assumptions have to be made to simplify the analysis. These are based on the idea that the reactive end groups and the catalyst are located in the amorphous regions. Polycondensations in the solid state are equilibrium reactions but are complicated by the two-phase character of the semicrystalline polymer. 

Syntheses of phenoxy-substituted polynaphthylimides and polyperyleneimides were carried out in accordance with Scheme 5.4 [37, 38]. All polycondensation reactions were carried out under high-temperature solution polycondensation conditions in phenolic solvents (w-cresol, m- or p-chlorophenols) using benzimidazole and benzoic acid as catalysts. All the reactions proceeded homogeneously and led to the formation of deeply coloured polymers. General properties of the polymers are listed in Table 5.6. 

Rhodium(I) complexes immobilized on silica using 3-(3-silylpropyl)-2,4-pentanedio-nato ligands (38) show good activity in the hydrosilylation of 1-octene with HSi(OEt)3 at 100°C60. The immobilized Rh catalysts are prepared by (i) reaction of (EtO)3Si(CH2)3C(COMe)2Rh(CO)2 with untreated silica (Catalyst A), (ii) reaction of Rh(acac)(CO)2 (acac = acetylacetonato = 2,4-pentanedionato) with silica modified by [(EtO)3Si(CH2)3C(COMe)2] prior to the complexation (Catalyst B), (iii) reaction of [Rh(CO)2Cl]2 with a polycondensate of [(EtO)3Si(CH2)3C(COMe)2] , Si(OEt)4 and water (Catalyst C) and (iv) sol-gel processing of (EtO)3Si(CH2)3C(COMe)2Rh(CO)2 and Si(OEt)4 (Catalyst D). The Catalysts A and B show ca three times better activity than their homogeneous counterparts, while the Catalyst D exhibits only low activity and the Catalyst C is inactive60. 

Incompletely cured networks constitute an important case of nonideal networks. They can be considered homogeneous if they result from step polycondensation. The following factors are expected to have an influence on Tg (beyond the gel point) ... 

Homogeneous IEM are produced either by polymerization of functional monomers (e.g., polycondensation of phenol or phenol-sulphonic acid with formaldehyde) or by functionalization of a polymer film by sulphonation of a polystyrene film. 

In homogeneous ion-exchange membranes the fixed-charged groups are evenly distributed over the entire membrane polymer matrix. Homogeneous membranes can be produced, for example, by polymerization or polycondensation of functional monomers such as phenolsulfonic acid, or by functionalizing a polymer such as polysulfone dissolved in an appropriate solvent by sulfonation. 

The salt monomer method was successfully applied to the preparation of the electrically-conducting polyimide-carbon black composites [62]. The composites are prepared as follows An aqueous solution of salt monomer 9PMA was mixed with carbon black, giving a suspension. This was evaporated to dryness under reduced pressure to afford a homogeneously-mixed powder composed of the salt monomer and carbon black. The powder was subjected to solid-state thermal polycondensation in the form of a pellet at 240 °C for 1 h under atmospheric pressure. The semiconducting aliphatic polyimides (P-9PM, Tm=315 °C) having electric conductivity of about 10"6 S/cm was readily obtained by mixing only 1 wt% of carbon black based on the polyimide. 

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