Polymer synthesis terephthalate

Further residual metal oxides from catalysts used for polymer synthesis, e.g. poly-terephthalic acid diol ester, are oxides of antimony, gallium, germanium, cobalt, man-... 

Terephthalic acid is usually converted directly to the dimethyl ester for polymer synthesis. This is prepared by superficially conventional technology using methanol and a mineral acid under moderate conditions (Eq. 19.67). 

With the introduction of oil-based polymers such as poly[ethylene], poly[propylene], poly[styrene], poly[ethylene terephthalate] and poly[vinyl chloride] the packaging industry has been truly revolutionised. Despite the advances in polymer synthesis and processing, their end of life still poses a problem [159]. The first choice for processing plastic waste is reuse, but only some plastics can be reused after proper processing, and... 

As described in detail in Sect. 2, furan-2,5-dicarboxylic acid (FDCA) 11 has drawn considerable attention in recent years as a renewable alternative to terephthalic acid for the production of phthalate polymers. Synthesis of FDCA from CMF was first reported by Fenton et al. by treatment with nitric acid [141]. Later, Brasholz et al. used the same method to obtain a 59% yield of FDCA [123]. 2,5-Diformylfuran 9 has also been prepared by nitric acid oxidation of CMF [148] (Scheme 15). 

The production and applications of polymers have gradually developed, gaining ground in many fields. The main classes of polymers, namely polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene and polyethylene terephthalate are produced in millions of tonnes annually [1]. There are many methods of polymer synthesis free-radical polymerisation (bulk, solution, emulsion and suspension), condensation polymerisation, ethoxylation, polymer compounding and formulations involving solvents, fillers, pigments and so on. Besides the high volume consumption of these common plastics, the demand for polymers with specific end-use properties has increased. 

If you take ethylene glycol, with its alcohol functional groups on both carbons, and react it with terephthalic acid, with its two organic acid functional groups, you can eliminate water and form the condensation polymer polyethylene terephthalate (PET), a polyester. Figure 16-7 shows the synthesis of PET. 

F, is a highly reactive but stable compound. It is structurally similar to terephthalic and isophthalic acid, which are monomeric units in the synthesis of petroleum-based, large-volume polymers. Thermally stable polyesters, polyamides and polyara-mides based on f represent present and future potential replacements for fossil raw materials in polymer synthesis. 

In 1954 the surface fluorination of polyethylene sheets by using a soHd CO2 cooled heat sink was patented (44). Later patents covered the fluorination of PVC (45) and polyethylene bottles (46). Studies of surface fluorination of polymer films have been reported (47). The fluorination of polyethylene powder was described (48) as a fiery intense reaction, which was finally controlled by dilution with an inert gas at reduced pressures. Direct fluorination of polymers was achieved in 1970 (8,49). More recently, surface fluorinations of poly(vinyl fluoride), polycarbonates, polystyrene, and poly(methyl methacrylate), and the surface fluorination of containers have been described (50,51). Partially fluorinated poly(ethylene terephthalate) and polyamides such as nylon have excellent soil release properties as well as high wettabiUty (52,53). The most advanced direct fluorination technology in the area of single-compound synthesis and synthesis of high performance fluids is currently practiced by 3M Co. of St. Paul, Minnesota, and by Exfluor Research Corp. of Austin, Texas. 

In 1975, the synthesis of the first main-chain thermotropic polymers, three polyesters of 4,4 -dihydroxy-a,a -dimethylbenzalazine with 6, 8, and 10 methylene groups in the aHphatic chain, was reported (2). Shortly thereafter, at the Tennessee Eastman Co. thermotropic polyesters were synthesized by the acidolysis of poly(ethylene terephthalate) by/ -acetoxybenzoic acid (3). Copolymer compositions that contained 40—70 mol % of the oxybenzoyl unit formed anisotropic, turbid melts which were easily oriented. 

Although poly(trimethylene terephthalate) has been known for many years it was only introduced by Shell in the late 1990s as a consequence of a breakthrough in the synthesis of the monomer 1,3-propane diol which enabled the polymer to be produced at costs suitable for commercialisation. The polymer itself is prepared by melt condensation of the diol with terephthalic acid. 

The partially aromatic PAs are exclusively made of die diamine-diacid type and not die amine-acid type. The aromatic diamines, similar to phenylene diamines, color easily and dieir polymers are conjugated, having a golden brown color. The aromatic diacids used in the formation of partially aromatic PAs are mainly terephthalic and isophthalic acids. Starting with the diacids, the PA salt is made first and with this the salt prepolymers are prepared. The prepolymerization is usually carried out in an autoclave to prevent die sublimation of the reactants. In a laboratory synthesis it would be preferable to avoid this autoclave step as one is not always available. It is possible to start with the more reactive esters, such as diphenyl isophtiialate, or with the acid chlorides starting with the reactive isocyanates is, in principle, also possible. The terephthalic and isophthalic acids are also used to modify PA-6,6 and PA-4,6 to more dimensionally stable copolymers.6,18... 

Poly(phenyleneethynylene)s, 482 optically active, 516-517 synthesis of, 496-500, 502 Poly(m-phenylene isophthalamide), 136 synthesis of, 185-186 Poly(l,4-phenylene terephthalate) liquid crystalline polymers, 51 Poly(para-phenylene)s, 472. See also Poly (p -pheny lene)... 

Polymer Recycling 3,No.3, 1997/98, p.173-80 UNSATURATED POLYESTER RESINS FROM POLY(ETHYLENE TEREPHTHALATE) WASTE SYNTHESIS AND CHARACTERISATION Abdel-Azim AA Mekewi M A Gouda S R Egyptian Petroleum Research Institute Ain Shams,University Egypt,Military Technical College... 

Walch E. and Caymans R.J., Synthesis and properties of poly(butylenes terephthalate)-b-polyisobutylene segmented block copolymers, Polymer, 35, 636, 1994. 

Polyesters, which are a class of engineering thermoplastics, are found in a wide variety of applications including carbonated drink bottles, fibers for synthetic fabrics, thin films for photographic films and food packaging, injection molded automotive parts, and housings for small appliances. In this chapter, we svill explore the synthesis of this class of polymers. We will also look at the typical properties and end uses for the most common of these resins, polyethylene terephthalate and polybutylene terephthalate, which are commonly known as PET and PBT, respectively. 

Oxidation is the first step for producing molecules with a very wide range of functional groups because oxygenated compounds are precursors to many other products. For example, alcohols may be converted to ethers, esters, alkenes, and, via nucleophilic substitution, to halogenated or amine products. Ketones and aldehydes may be used in condensation reactions to form new C-C double bonds, epoxides may be ring opened to form diols and polymers, and, finally, carboxylic acids are routinely converted to esters, amides, acid chlorides and acid anhydrides. Oxidation reactions are some of the largest scale industrial processes in synthetic chemistry, and the production of alcohols, ketones, aldehydes, epoxides and carboxylic acids is performed on a mammoth scale. For example, world production of ethylene oxide is estimated at 58 million tonnes, 2 million tonnes of adipic acid are made, mainly as a precursor in the synthesis of nylons, and 8 million tonnes of terephthalic acid are produced each year, mainly for the production of polyethylene terephthalate) [1]. 

Step-growth condensation polymers, such as polyesters and polyamides, are formed by reversible reactions. In the case of PET, the commercial synthesis is essentially carried out by two reactions. The first is the formation of bishydroxyethyl terephthalate by esterification of a diacid with a glycol or by transesterification of a diester with a glycol. The second is the formation of the polymer by a polycondensation reaction. 

Daiguebonne, C. Kerbellec, N. Bernot, K. Gerault, Y. Deluzet, A. Guillou, O. Synthesis, Crystal Structure, and Porosity Estimation of Hydrated Erbium Terephthalate Coordination Polymers. Inorg Chem. 2006, 45, 5399-5406. 

Table 9.2 summarizes the uses of acetic acid. Vinyl acetate is another top 50 chemical. Acetic anhydride is used to make cellulose acetate and at times has been in the top 50 chemicals itself. Cellulose acetate is a polymer used mainly as a fiber in clothing and cigarette filters. Ethyl acetate is a common organic solvent. Acetic acid is used as a solvent in the manufacture of terephthalic acid (TA) and dimethyl terephthalate (DMT), which are monomers for the synthesis of poly(ethylene terephthalate), the polyester of the textile industry. A minor household use of acetic acid is as a 3-5% aqueous solution, which is called vinegar. 

For most step polymerizations, for example, in the synthesis of polyl hexamethylene adipa-mide) or polyethylene terephthalate), two reactants or monomers are used in the process, and the polymer obtained contains two different kinds of structures in the chain. This is not the case for chain polymerizations, where only one monomer need be used to produce a polymer. However, chain polymerizations can be carried out with mixtures of two monomers to form polymeric products wiht two different structures in the polymer chain. This type of chain polymerization process in which two monomers are simultaneously polymerized is termed a copolymerization, and the product is a copolymer. It is important to stress that the copolymer is not an alloy of two homopolymers hut contains units of both monomers incorporated into each copolymer molecule. The process can be depicted as... 

Lee CW, Do Chung J (2009) Synthesis and biodegradation behavior of poly(ethylene terephthalate) oligomers. Polymer (Korea) 33 198-202... 

Condensation monomers having the benzimidazolin-2-one ring system have found utility as modifiers in polyester synthesis. In particular, halogenated diols (73) and dicarboxylic acids (74) may be incorporated (78MI11100) into polyethylene terephthalate) or poly(butyl-ene terephthalate) at fairly low levels to impart flame retardancy. This can be accomplished without adverse effects upon other polymer properties. 

This synthesis was carried out by reaction of polyethylene terephthalate and ethylenediamine in the presence of the metallic salts. Mechanical activation was supplied by vibratory milling in a nitrogen atmosphere. Granular polyethylene terephthalate (supplied by U.F.S.-Jassy) was subjected to mechanical processing in powdered form. It was purified by dissolving in a 40/60 phenol/chloroform mixture and reprecipitating with methanol. After filtration, the polymer was extracted... 

---