Cyclic terephthalate esters

Scheme 3.1 Preparation of cyclic terephthalate esters via acid chlorides or depolymerization, and polymerization to high-molecular-weight polymer...

In 1930, in one of many pioneering studies, Carothers showed that certain condensation polymers could be cyclic or macrocyclic rather than exclusively linear. In addition to this very important observation, he showed that thermolysis in vacuo of certain polymers could also yield macrocyclic materials. Quite a number of papers have been published on this subject since that time, especially dealing with the chemistry of phthalate " , isophthalate " ", and terephthalate esters Many of these structures are tabulated at the end of this... 

Voltammetric data for ester reductions are available for several aromatic esters [51-54], and in particular cyclic voltammetry shows clearly that in the absence of proton donors reversible formation of anion radical occurs [51]. In dimethylfonnamide (DMF) solution the peak potential for reduction of methyl benzoate is —2.29 V (versus SCE) for comparison dimethyl terephthalate reduces at —1.68 V and phthalic anhydride at —1.25 V [4]. Half-wave potentials for reduction of aromatic carboxylate esters in an unbuffered solution of pH 7.2 are linearly correlated with cr values [51] electron-withdrawing substituents in the ring or alkoxy group shift Ei/o toward less negative potentials. Generally, esters seem to be more easily reducible than the parent carboxylic acids. Anion radicals of methyl, ethyl, and isopropyl benzoate have been detected by electron paramagnetic resonance (epr) spectroscopy upon cathodic reduction of these esters in acetonitrile-tetrapro-pylammonium perchlorate [52]. The anion radicals of several anhydrides, including phthalic anhydride, have similarly been studied [55]. 

A number of studies were done to assess thermal stability of aromatic polyesters. Some of these studies describe flash pyrolysis [27-32]. Some studies are dedicated to slow thermal degradation in an inert atmosphere, and others describe the decomposition in specific conditions such as in the presence of humidity or in the presence of catalysts [33]. For example, thermal decomposition of poly(butylene terephthalate) was significantly influenced by the presence of water vapor, and the amount of the residues decrease with increasing the partial pressure of water in the atmosphere [34]. In another study, thermal stability of some small molecule phthalate esters was studied [35]. The results can be used for inferring information on the thermal stability of related polymers. The influence of substitution on the p-carbon atom was evaluated on compounds such as bis(2-aminobutyl) phthalate, bis(2-nitrobutyl) phthalate, bis(2,4-diphenylbutyl) phthalate, and dineopentyl phthalate. Only the phenyl groups were found to improve the heat resistance by the obstruction of the planar configuration necessary for the c/s-elimination and the hindrance of the formation of a six-membered cyclic transition state. 

Aromatic polyesters were enzymatically synthesized under mild reaction conditions. Divinyl esters of isophthalic acid, terephthalic acid, and p-phen-ylene diacetic acid were polymerized with glycols by lipase CA catalyst to give polyesters containing an aromatic moiety in the main chain.208 In the lipase-catalyzed polymerization of dimethyl isophthalate and 1,6-hexanediol in toluene with nitrogen bubbling, a mixture of linear and cyclic polymers was formed.209 High molecular weight aromatic polyester (Mw 5.5 x 104) was synthesized by the lipase CA-catalyzed polymerization of isophthalic acid and 1,6-hexanediol under vacuum.210 Enzymatic polymerization of divinyl esters and aromatic diols also afforded the aromatic polyesters.211... 

Polymer plasticization can be achieved either through internal or external incorporation of the plasticizer into the polymer. Internal plasticization involves copolymerization of the monomers of the desired polymer and that of the plasticizer so that the plasticizer is an integral part of the polymer chain. In this case, the plasticizer is usually a polymer with a low Tg. The most widely used internal plasticizer monomers are vinyl acetate and vinylidene chloride. External plasticizers are those incorporated into the resin as an external additive. Typical low-molecular-weight external plasticizers for PVC are esters formed from the reaction of acids or acid anhydrides with alcohols. The acids include ortho- and iso-or terephthalic, benzoic, and trimellitic acids, which are cyclic or adipic, azeleic, sebacic, and phosphoric acids, which are linear. The alcohol may be monohydric such as 2-ethylhexanol, butanol, or isononyl alcohol or polyhydric such as ethylene or propylene glycol. The structures of some plasticizers of PVC are shown in Table 9.1. 

Based on model reactions for the preparation of poly(ethylene terephthalate) by ester interchange, the optimum molar ratio of ethvlene glycol to dimethyl terephthalate is 2.4 to 1. This ratio allows complete removal of methanol. The overall polyesteiification reaction is third order. In addition, high molecular weight polymerizations of poly(ethylene terephthalate) invariably produce some cyclic oligomers as byproducts. Eight different cyclic species were identified in one commercial polymer ... 

The thermal degradation of poly(butylene terephthalate) was examined with the aid of a laser microprobe and mass spectrometry [506]. A complex multistage decomposition mechanism was observed that involves two reaction paths. The initial degradation takes place by an ionic mechanism. This results in an evolution of tetrahydrofuran. This is followed by concerted ester pyrolyses reactions that involve intermediate cyclic transition states and result in formation of 1,3-butadiene. Simultaneous decarboxylations occur in both decomposition paths. The latter stages of decomposition are... 

Poly(ethylene terephthalate) is the condensation polymer made from terephthalic acid and ethylene glycol. The acid or its dimethyl ester is obtained by the oxidation of -xylene, a product from catalytic reforming of naphtha. The glycol is obtained from ethane via the corresponding cyclic oxide. With the availability of purified terephthalic acid since the 1960s direct esterification of the acid in a continuous process is used in commercial production of the polyester [31] ... 

Macrocyclic oligomer precursors of polycarbonates, PET, polymers of amides, etherketones, and ethersulfones are candidates for further study of macrocyclic oligomer polymerization thermodynamics [6]. Research extends to cyclic arylates (cyclic aryl-aryl esters) and cyclic alkyl aryl esters going back to isolating a cyclic trimer of poly(ethylene-terephthalate) in 1954 [13]. Much of the work on macrocyclic oligomers as precursors to high-MW macromolecules starts with spiro(bis)indane (SBI) biphenyl monomer to produce macrocyclic carbonates. 

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