Polymer terephthalate

Adipic acid dimethyi adipate (polyesters), acrylamide (acrylonitrile co-polymers), acrylonitrile (acrylamide co-polymers), acrylic acid (acrylic polymers), buta-1,3-dlene (PS co-polymers, elastomers), butan-1,4-diol (polyesters), 2,2-bis(4-hydroxyphenyl)butan-1-ol (polyesters), 1,1-bis(4-hydroxyphenyl)cyclohexane (polyesters), 4,4 -(propane-2,2-diyl)-dlphenol known as bisphenol A (polyesters), ethyleneglycol (polyestere), formaldehyde (phenol-formaldehyde resins), isophthalic acid (PET), caprolactame and C -C,2 aminocar-boxyllc acids and their lactames (polyamides), melamine (amino-formaldehyde resins), methacryllc acid and methyl methacrylate (acrylic polymers), methylstyrene (PS and co-polymers), propyleneglycol (polyesters), sebacic acid and dimethyl sebacate (polyesters), styrene (PS and co-polymers), terephthalic acid and dimethyl terephthalate (PET), vinyl acetate (vinyl acetate co-polymers), vinyl chloride (PVC and co-polymers), vinylldenechlorlde (PVdC and co-polymers)... 

Glass transition temperature of uncrosslinked polymer Terephthalic acid T riphenylphosphite... 

Condensation polymerization differs from addition polymerization in that the polymer is formed by reaction of monomers, each step in the process resulting in the elimination of some easily removed molecule (often water). E.g. the polyester polyethylene terephthalate (Terylene) is formed by the condensation polymerization (polycondensation) of ethylene glycol with terephthalic acid ... 

PCTA Copolyester. Poly(l,4-cyclohexanedimethylene terephthalic acid) (PCTA) copolyester is a polymer of cyclohexanedimethanol and terephthalic acid, with another acid substituted for a portion of the terephthalic acid otherwise required. It has the following formula ... 

Those polymers which are the condensation product of two different monomers are named by applying the preceding rules to the repeat unit. For example, the polyester formed by the condensation of ethylene glycol and terephthalic acid is called poly(oxyethylene oxyterphthaloyl) according to the lUPAC system, as well as poly (ethylene terephthalate) or polyethylene terephthalate. 

Ester interchange reactions are valuable, since, say, methyl esters of di-carboxylic acids are often more soluble and easier to purify than the diacid itself. The methanol by-product is easily removed by evaporation. Poly (ethylene terephthalate) is an example of a polymer prepared by double application of reaction 4 in Table 5.3. The first stage of the reaction is conducted at temperatures below 200°C and involves the interchange of dimethyl terephthalate with ethylene glycol... 

The windows of the absorption cell are made from polymer material such as polyethylene, poly(ethylene terephthalate Terylene ) or polystyrene. 

Most of the polymer s characteristics stem from its molecular stmcture, which like POE, promotes solubiUty in a variety of solvents in addition to water. It exhibits Newtonian rheology and is mechanically stable relative to other thermoplastics. It also forms miscible blends with a variety of other polymers. The water solubiUty and hot meltable characteristics promote adhesion in a number of appHcations. PEOX has been observed to promote adhesion comparable with PVP and PVA on aluminum foil, cellophane, nylon, poly(methyl methacrylate), and poly(ethylene terephthalate), and in composite systems improved tensile strength and Izod impact properties have been noted. 

Reactions of the Methyl Groups. These reactions include oxidation, polycondensation, and ammoxidation. PX can be oxidized to both terephthahc acid and dimethyl terephthalate, which ate then condensed with ethylene glycol to form polyesters. Oxidation of OX yields phthaUc anhydride, which is used in the production of esters. These ate used as plasticizers for synthetic polymers. MX is oxidized to isophthaUc acid, which is also converted to esters and eventually used in plasticizers and resins (see Phthalic acids and otherbenzenepolycarboxylic acids). 

Uses. The largest uses of butanediol are internal consumption in manufacture of tetrahydrofuran and butyrolactone (145). The largest merchant uses are for poly(butylene terephthalate) resins (see Polyesters,thermoplastic) and in polyurethanes, both as a chain extender and as an ingredient in a hydroxyl-terminated polyester used as a macroglycol. Butanediol is also used as a solvent, as a monomer for vadous condensation polymers, and as an intermediate in the manufacture of other chemicals. 

The Textile Eiber Product Identification Act (TEPIA) requires that the fiber content of textile articles be labeled (16). The Eederal Trade Commission estabhshed and periodically refines the generic fiber definitions. The current definition for a polyester fiber is "A manufactured fiber ia which the fiber-forming substance is any long-chain synthetic polymer composed of at least 85% by weight of an ester of a substituted aromatic carboxyUc acid, including but not restricted to terephthalate units, and para substituted hydroxyben2oate units."... 

Terephthahc acid (TA) or dimethyl terephthalate [120-61 -6] (DMT) reacts with ethyleae glycol (2G) to form bis(2-hydroxyethyl) terephthalate [959-26-2] (BHET) which is coadeasatioa polymerized to PET with the elimination of 2G. Moltea polymer is extmded through a die (spinneret) forming filaments that are solidified by air cooling. Combinations of stress, strain, and thermal treatments are appHed to the filaments to orient and crystallize the molecular chains. These steps develop the fiber properties required for specific uses. The two general physical forms of PET fibers are continuous filament and cut staple. 

The film tube is collapsed within a V-shaped frame of rollers and is nipped at the end of the frame to trap the air within the bubble. The nip roUs also draw the film away from the die. The draw rate is controlled to balance the physical properties with the transverse properties achieved by the blow draw ratio. The tube may be wound as such or may be sHt and wound as a single-film layer onto one or more roUs. The tube may also be direcdy processed into bags. The blown film method is used principally to produce polyethylene film. It has occasionally been used for polypropylene, poly(ethylene terephthalate), vinyls, nylon, and other polymers. 

BiaxiaHy oriented films have excellent tensile strength properties and good tear and impact properties. They are especially well regarded for their brilliance and clarity. Essentially all poly(ethylene terephthalate) film is biaxiaHy oriented, and more than 80% of polypropylene film is biaxiaHy oriented. Polystyrene film is oriented, and a lesser amount of polyethylene, polyamide, poly(vinyl chloride), and other polymers are so processed. Some of the specialty films, like polyimides (qv), are also oriented. 

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. 

Other Polymers. Besides polycarbonates, poly(methyl methacrylate)s, cycfic polyolefins, and uv-curable cross-linked polymers, a host of other polymers have been examined for their suitabiUty as substrate materials for optical data storage, preferably compact disks, in the last years. These polymers have not gained commercial importance polystyrene (PS), poly(vinyl chloride) (PVC), cellulose acetobutyrate (CAB), bis(diallylpolycarbonate) (BDPC), poly(ethylene terephthalate) (PET), styrene—acrylonitrile copolymers (SAN), poly(vinyl acetate) (PVAC), and for substrates with high resistance to heat softening, polysulfones (PSU) and polyimides (PI). 

The more familiar source-based names for these polymers are poly(phenylene oxide) (1), poly(ethylene terephthalate) (2), and polycaprolactam (3). 

Fig. 4. The Amoco purification process for polymer-grade terephthalic acid.

Hydrolysis of Dimethyl Terephthalate. Hoechst Celanese and Eormosa Chemical Eibers Corp. produce a polymer-grade terephthahc acid by hydrolysis of high purity dimethyl terephthalate. Hbls-Troisdorf AG hcenses a process with this step (70). Hydrolysis occurs at 260—280°C and 4500—5500 kPa (45—55 atm) in a hydrolysis reactor without catalysis. The overhead methanol and water vapor is separated and the methanol is returned to the dimethyl terephthalate section for reuse. The reactor hquid is crystallized, cycloned, washed, and further cooled. Einahy, the slurry is centrifuged and dried. The product has less than 25 ppm of 4-formylbenzoic acid and very low levels of other impurities. There may be several hundred parts per million of monomethyl terephthalate, which is incompletely hydrolyzed dimethyl terephthalate. 

Table 20. Specifications for Polymer-Grade Terephthalic Acid...

Small amounts of polymer-grade terephthaHc acid and dimethyl terephthalate are used as polymer raw materials for a variety of appHcations, eg, adhesives and coatings. They are also used to make high performance polymers or engineering resins. Poly(ethylene terephthalate) is itself an engineering resin, although one more widely used is poly (butylene) terephthalate, formed by reaction with 1,4-butanediol as the comonomer. 

The packaging (qv) requirements for shipping and storage of thermoplastic resins depend on the moisture that can be absorbed by the resin and its effect when the material is heated to processing temperatures. Excess moisture may result in undesirable degradation during melt processing and inferior properties. Condensation polymers such as nylons and polyesters need to be specially predried to very low moisture levels (3,4), ie, less than 0.2% for nylon-6,6 and as low as 0.005% for poly(ethylene terephthalate) which hydrolyzes faster. 

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