Melt polymerizations

Glycolysis is claimed to be somewhat less cosdy than methan olysis (33). Depolymerization is not taken completely to monomers (34). Rather, recovered PET is depolymerized to low molecular weight oligomers. Contaminants are removed using proprietary technology. The oligomers are then fed to a melt polymerization vessel in which PET is produced. 

Condensation ofDianhydrides with Diamines. The preparation of polyetherknides by the reaction of a diamine with a dianhydride has advantages over nitro-displacement polymerization sodium nitrite is not a by-product and thus does not have to be removed from the polymer, and a dipolar aprotic solvent is not required, which makes solvent-free melt polymerization a possibiUty. Aromatic dianhydride monomers (8) can be prepared from A/-substituted rutrophthalimides by a three-step sequence that utilizes the nitro-displacement reaction in the first step, followed by hydrolysis and then ring closure. For the 4-nitro compounds, the procedure is as follows. 

Bisphenol A Polycarbonate Resins. These resins are manufactured by interfacial polymerization (84,85). A small amount of resin is produced by melt-polymerization of bisphenol with diphenyl carbonate in Russia and the People s RepubHc of China. Melt technology continues to be developmental in Japan and the West, but no commercial activities have started-up to date, although some were active in the late 1960s. No reports of solvent-based PC manufacture have been received. 

The main method of PA synthesis is by melt polymerization. The polymerization of PA-6,6 occurs in two stages, a prepolymerization of the PA salt at elevated pressures followed by a melt polymerization at atmospheric pressure. The prepolymerization stage requires an autoclave, preferably with a glass insert. The glass insert allows easy extraction of the polymer. PA-6 polymerization is simple it can be carried out at atmospheric pressure, and the evaporating water stirs the reaction medium. 

At atmospheric or reduced pressure, a melt polymerization on a small scale (25-100 g) can easily be carried out using straight-wall flange flasks (250 mL) (Fig. 3.18a). The straight wall often allows the extraction of the polymer from... 

Figure 3.18 Laboratory melt polymerization setup (a) 250 mL (b) 50-mL reactor in either oil bath or heating block.

At moderately high molecular weights, the reaction mass becomes highly viscous, which limits heat transfer and evaporation of the condensation water. This high viscosity limits further melt polymerization in the bulk. In the literature, the melt polymerization stage is sometimes omitted and the prepolymers are condensed to high molecular weights in the solid state.6,28 41 The polymerizations can easily be carried out without a catalyst. 

Starting with caprolactam, an initiator is required for the hydrolytic melt polymerization this can be any of the following water, >-amino acids, acids, diacids,... 

The kinetics of the melt-polymerization of nylon 6,6 is third order (1)... 

The conventional route to prepare I generally involves a high temperature melt polymerization of hexachlorocyclotriphosphazene, or trimer (IV). Recent studies have demonstrated the effectiveness of various acids and organometalllcs as catalysts for the polymerization of IV (8). Alternate routes for the preparation of chloro-polymer which do not involve the ring opening polymerization of trimer have been reported in the patent literature (9. 10). These routes involve a condensation polymerization process and may prove to be of technological importance for the preparation of low to moderate molecular weight polyphosphazenes. 

Diphenylcarbonate (DPC) is a key monomer for producing LEXAN polycarbonate resin by melt polymerization reaction of DPC with Bisphenol A. Currently, DPC is produced by General Electric Company (GE) in Cartagena, Spain, using a two-step process (Eq. 1) The stoichiometric carbonylation of... 

The polymerization reaction (Figure I) is markedly influenced by the presence of trace impurities which was one of the difficulties encountered in earlier investigations. The conventional route is a melt polymerization of highly purified trimer (NPC1 ), or a mixture of trimer and a small amount of tetramer (NFCl.), sealed under vacuum in glass ampoules, at approximately 250°C. Proper selection of time and temperature is necessary to obtain II and avoid the formation of cross-linked matrix (III). 

Figure 2. GPC studies of melt polymerized poly(dichlorophosphazene). Cumulative C(M) and differential F(log M) MWD of II obtained at 60 and 100 h. Ref. 20.

Cyclic enone, 12 185 Cyclic ethers, 10 567, 569 12 663 polymerization, 14 271 Cyclic fatigue, in ceramics, 5 633-634 Cyclic gas generators, 6 786-787, 789, 827 Cyclic halides, 19 56 Cyclic hexakis(thio-l,4-phenylene), melt polymerization of, 23 705 Cyclic hydrocarbons, 13 687 Cyclic hydroxyalkyl alkyl peroxide, 18 454 Cyclic ion exchange operation, 14 408-413 Cyclic ketones, 12 176, 177 14 590-592. See also Cyclic 1,2-diketones physical properties of, 14 591t hydroxyalkyl hydroperoxides from, 18 450... 

Low level wastes (LLW), 23 592. See also Low-level radioactive waste (LLW) from reactors, 77 598 Low-melting lead alloys, 14 779 Low-melting-point indium alloys, 14 196 Low-melting thiodiols, DBTDL-catalyzed step-growth solution and melt polymerization reaction of, 23 744 Low-methoxyl pectins (LM pectins), 4 728 13 69... 

Finally, Nagahata et al. have reported polymerization of PET cyclic dimer [16], The latter is a minor component in PET cyclics, normally present at less than 10 % of the total cyclics made either from acid chlorides or via depolymerization. Nagahata et al. report melt polymerization at 250-325 °C, leading to an Mw ... 

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