Polyester solubility

Hydroquinone polyesters Soluble polymers with melting points of 335°C (635°F) to over 400° C (752°F). 

Polyesters are not different from other polymers, and any of the characterization methods commonly used in polymer science can obviously be applied to polyesters and provide information on their structure and properties. In this section, some data specific to polyesters—solubility information, COOH and OH endgroup titration, and infrared (IR) and NMR spectra assignments—are briefly summarized. Most of these data originate from the authors laboratory. References are provided on some particular points only. 

Siemann (27) recently determined the solubility parameters and densities of a group of biodegradable polyesters. Solubility parameters... 

Solubility, Crystallinity, and Compatibility. Polyester solubility is largely determined by the nature and proportions of the constituent monomers. Polyesters with a regular structure are crystalline. Examples of highly crystalline polyesters are poly(ethylene terephthalate) and poly(butylene terephthalate). Although medium to highly crystalline copolyesters are insoluble in paint solvents, they can be processed into adhesives and paints in the hot-melt process [2.87]. Slightly crystalline copolyesters are soluble, for example, in ketones and are mainly used for laminate adhesives. 

Further studies of the Yokozawa group concerned CCPs of aromatic polyesters. At first, polymerizations of 4-trimethylsiloxybenzoyl chloride and its anion (see Formula 16.7), first reported by Yokozawa et al. [110] were studied Yet the insolubility of poly(oxibenzoate) in aU inert solvents prevented a satisfactory characterization of the reaction products [111]. Therefore, a new class of monomers (see Formula 16.7d) was synthesized. The aliphatic side chains rendered the polyesters soluble in various inert solvents, and the activated heterocyclic amid group eased purification by recrystallization To prevent transesterilication the polymerization temperature had to be lowered to 30 °C [112, 113]. 

Polyester fibers have exceUent resistance to soap, detergent, bleach, and other oxidiziag agents. PET fibers are generally iasoluble ia organic solvents, including cleaning fluids, but are soluble ia some phenoHc compounds, eg, (9-chlorophenol. 

Vinyl organosol coatings, which incorporate a high molecular weight thermoplastic PVC organosol dispersion resin, are extremely flexible. Soluble thermosetting resins, including epoxy, phenoHc, and polyesters, are added to enhance the film s product resistance and adhesion. 

Properties. As prepared, the polymer is not soluble in any known solvents below 200°C and has limited solubiUty in selected aromatics, halogenated aromatics, and heterocycHc Hquids above this temperature. The properties of Ryton staple fibers are in the range of most textile fibers and not in the range of the high tenacity or high modulus fibers such as the aramids. The density of the fiber is 1.37 g/cm which is about the same as polyester. However, its melting temperature of 285°C is intermediate between most common melt spun fibers (230—260°C) and Vectran thermotropic fiber (330°C). PPS fibers have a 7 of 83°C and a crystallinity of about 60%. 

Examples of polymers which form anisotropic polymer melts iaclude petroleum pitches, polyesters, polyethers, polyphosphaziaes, a-poly- -xyljlene, and polysdoxanes. Synthesis goals iaclude the iacorporation of a Hquid crystal-like entity iato the maia chaia of the polymer to iacrease the strength and thermal stabiHty of the materials that are formed from the Hquid crystal precursor, the locking ia of Hquid crystalline properties of the fluid iato the soHd phase, and the production of extended chain polymers that are soluble ia organic solvents rather than sulfuric acid. 

A polyester-type fluorescent resin matrix (22) is made by heating trimellitic anhydride, propylene glycol, and phthaUc anhydride with catalytic amounts of sulfuric acid. Addition of Rhodamine BDC gives a bright bluish red fluorescent pigment soluble in DME and methanol. It has a softening point of 118°C. Exceptional heat resistance and color brilliance are claimed for products of this type, which are useful for coloring plastics. 

The di(hydroxyaLkyl) peroxide (2) from cyclohexanone is a soHd which is produced commercially. The di(hydroxyaLkyl) peroxide (2) from 2,4-pentanedione (11, n = 1 X = OH) is a water-soluble soHd which is also produced commercially (see Table 5). Both these peroxides are used for curing cobalt-promoted unsaturated polyester resins. Because these peroxides are susceptible to promoted decomposition with cobalt, they must exist in solution as equihbrium mixtures with hydroperoxide stmctures (122,149). 

Catalyst Selection. The low resin viscosity and ambient temperature cure systems developed from peroxides have faciUtated the expansion of polyester resins on a commercial scale, using relatively simple fabrication techniques in open molds at ambient temperatures. The dominant catalyst systems used for ambient fabrication processes are based on metal (redox) promoters used in combination with hydroperoxides and peroxides commonly found in commercial MEKP and related perketones (13). Promoters such as styrene-soluble cobalt octoate undergo controlled reduction—oxidation (redox) reactions with MEKP that generate peroxy free radicals to initiate a controlled cross-linking reaction. 

TrimeUitic anhydride is converted to PVC plasticizers, polyesters, water-soluble alkyd coatings, and polyamide—imide resias. The trimellitate plasticizers have a lower volatility than those derived from phthaUc anhydride (see Plasticizers). 

This mixture is known as Quinoline Yellow A [8003-22-3] (Cl 47000) and is most widely used with polyester fibers (109). Upon sulfonation, the water-soluble Quinoline Yellow S or Acid Yellow 3 [8004-92-0] (Cl 47005) is obtained. This dye is used with wool and its aluminum salt as a pigment. Foron Yellow SE-3GL (Cl Disperse Yellow 64) is the 3-hydroxy-4-bromo derivative. Several other quinoline dyes are commercially available and find apphcations as biological stains and analytical reagents (110). 

Some polymers from styrene derivatives seem to meet specific market demands and to have the potential to become commercially significant materials. For example, monomeric chlorostyrene is useful in glass-reinforced polyester recipes because it polymerizes several times as fast as styrene (61). Poly(sodium styrenesulfonate) [9003-59-2] a versatile water-soluble polymer, is used in water-poUution control and as a general flocculant (see Water, INDUSTRIAL WATER TREATMENT FLOCCULATING AGENTs) (63,64). Poly(vinylhenzyl ammonium chloride) [70304-37-9] h.a.s been useful as an electroconductive resin (see Electrically conductive polya rs) (65). 

The alkaline solutions can remove water-soluble polymers in the spinning mix and inert products such as titanium dioxide. Basic treatments can also hydroly2e a certain amount of the polyester itself. For some silk-like appHcations or for producing fine denier fabrics, this basic treatment can produce a 10—30% weight loss of polyester (190,196). Certain polyesters such as anionically modified polyester can undergo more rapid weight loss than regular polyester (189). 

Some commercial durable antistatic finishes have been Hsted in Table 3 (98). Early patents suggest that amino resins (qv) can impart both antisHp and antistatic properties to nylon, acryUc, and polyester fabrics. CycHc polyurethanes, water-soluble amine salts cross-linked with styrene, and water-soluble amine salts of sulfonated polystyrene have been claimed to confer durable antistatic protection. Later patents included dibydroxyethyl sulfone [2580-77-0] hydroxyalkylated cellulose or starch, poly(vinyl alcohol) [9002-86-2] cross-linked with dimethylolethylene urea, chlorotria2ine derivatives, and epoxy-based products. Other patents claim the use of various acryUc polymers and copolymers. Essentially, durable antistats are polyelectrolytes, and the majority of usehil products involve variations of cross-linked polyamines containing polyethoxy segments (92,99—101). 

Hydrophobic fibers are difficult to dye with ionic (hydrophilic) dyes. The dyes prefer to remain in the dyebath where they have a lower chemical potential. Therefore nonionic, hydrophobic dyes are used for these fibers. The exceptions to the rule are polyamide and modified polyacrylonitriles and modified polyester where the presence of a limited number of ionic groups in the polymer, or at the end of polymer chains, makes these fibers capable of being dyed by water-soluble dyes. 

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