Sulfonated Polyesters

It has been demonstrated that sulfonated terephthalate units contribute significantly to the biodegradabihty of the polymer (59). Bio- 

However, it has been stated that when even blends can reach a desirable balance of physical and thermal properties, the use of polymeric blends will complicate the processes used to produce the final products (60). Therefore, single products will be more desirable. 

Sulfonated aUphatic-aromatic polyesters include polyesters derived from a mixture of aliphatic dicarboxyUc adds and aromatic dicarboxyUc acids and a sulfonated monomer, such as a salt of 5-sulfoisophthaUc acid. Suitable dicarboxyUc adds are summarized in Table 4.10. 

7- Naphthalenedicarboxylic acid 3,4 -Diphenyl ether dicarboxyUc acid 4,4 -Diphenyl ether dicarboxyUc acid 3,4 -Diphenyl sulfide dicarboxyUc acid 4,4 -Diphenyl sulfide dicarboxyUc acid 3,4 -Diphenyl sulfone dicarboxyUc acid 4,4 -Diphenyl sulfone dicarboxyUc acid 3,4 -Benzophenonedicarboxylic acid 4,4 -Benzophenonedicarboxylic acid 1,4-Naphthalene dicarboxyUc acid 

Oxalic acid Malonic acid Succinic acid Glutaric acid Adipic acid Pimelic acid Suberic acid Azelaic acid Sebacic acid Brassylic acid Docosanedioic acid Undecanedioic acid Tetracosanedioic acid Hexadecanedioic acid 

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Sulfonated polyesters, 23 536 Sulfonated polymers, 23 534-536 Sulfonated polystyrene membranes, 23 720 Sulfonated products... 

More recently, a new series of water dispersed anionic polymers, the AQ 29D, 38D and 55D polymers were released by Eastman Kodak. Since that time, these polymers were used as electrode modifier (12, 13), as covering membrane (14) and as support for enzyme immobilization (15, 16). AQ polymers are high molecular weights (14,000 to 16,000 Da) sulfonated polyester type polymers (17, 18). Their possible structures have been recently presented (18). The AQ polymer serie shows many interesting characteristics useful for the fabrication of biosensors. They are water dispersed polymers and thus compatible with enzymatic activity. They have sulfonated pendant groups similar to Nafion and they can act as a membrane barrier for anionic interferring substances and they offer the possibility to immobilize redox mediators by ion exchange. 

In an earlier investigation by the author [3] sulfonated polyesters were prepared consisting of ethylene glycol and terephthalate acid capped with dimethyl-5-sulfoterephthalate. 

Geropon . [Rhone-Poulenc Surf. Rhone-Poulenc Geronazzo SpA] Sul-fosuccinates, sulfosuccinamates, tau-rates, isethionates, or sulfonated polyester emulsifier, wetting agent suspending r ent dispersant stabili for emulsion polymerization, pesticides, inks, textiles, paints. 

Table 4.10 DicarboxyUc acid Monomers and Monomers Suitable for Sulfonated Polyesters (60)...

The sulfonated aliphatic-aromatic copolyesters exhibit improved thermal properties, in particular, a desirable balance of high temperature properties and improved compostabUity Sulfonated polyesters can be prepared as follows (60) ... 

Several other methods for the preparation of sulfonated polyesters have been disclosed (61). 

Sulfonated Polyesters may be also used for water-dispersible fibers (63). The fibers contain a single or a blend of a sulfopoly-ester with a water-dispersible polymer. The multicomponent fibers can be used to produce microdenier fibers. The biodegradability of the polymers have been assessed by the ASTM Standard Method D6340-98 (64). 

SEM images of surface of (a) virgin and (b)Ti02-dip-coatedTFC-SR (thin film composite selective rejection) composite RO membrane (Fluid Systems Company). Membrane material PVA/polyaryl sulfone/ polyester. (Reprinted from Madaeni and Ghaemi, 2007 with permission from Elsevier.)... 

Sulfonated polyester polymer Sulfonated poly(styrene)... 

For systems of rigid poly diacetylenes with functional or ionic side groups and car-boxylated or sulfonated polystyrene or sulfonated polyester-urea urethanes, molecular composites could be achieved by ionic interactions [51]. The blends exhibited no microphase separation and the miscibility on a molecular length scale was proven by infrared spectroscopic, dynamic mechanical and differential scanning calorimetry analysis. The molecular reinforcement amounted to up to 1 order of magnitude in compliance with a Halpin Tsai description and was achieved by only a few weight percent of the rigid compound. 

Tg measurements have been performed on many other polymers and copolymers including phenol bark resins [71], PS [72-74], p-nitrobenzene substituted polymethacrylates [75], PC [76], polyimines [77], polyurethanes (PU) [78], Novolac resins [71], polyisoprene, polybutadiene, polychloroprene, nitrile rubber, ethylene-propylene-diene terpolymer and butyl rubber [79], bisphenol-A epoxy diacrylate-trimethylolpropane triacrylate [80], mono and dipolyphosphazenes [81], polyethylene glycol-polylactic acid entrapment polymers [82], polyether nitrile copolymers [83], polyacrylate-polyoxyethylene grafts [84], Novolak type thermosets [71], polyester carbonates [85], polyethylene naphthalene, 2,6, dicarboxylate [86], PET-polyethylene 2,6-naphthalone carboxylate blends [87], a-phenyl substituted aromatic-aliphatic polyamides [88], sodium acrylate-methyl methacrylate multiblock copolymers [89], telechelic sulfonate polyester ionomers [90], aromatic polyamides [91], polyimides [91], 4,4"-bis(4-oxyphenoxy)benzophenone diglycidyl ether - 3,4 epoxycyclohexyl methyl 3,4 epoxy cyclohexane carboxylate blends [92], PET [93], polyhydroxybutyrate [94], polyetherimides [95], macrocyclic aromatic disulfide oligomers [96], acrylics [97], PU urea elastomers [97], glass reinforced epoxy resin composites [98], PVOH [99], polymethyl methacrylate-N-phenyl maleimide, styrene copolymers [100], chiral... 

Naphthalenediol. This diol is prepared by the alkah fusion of 2-hydroxynaphthalene-6-sulfonic acid (Schaffer acid) at 290—295°C. Schaffer acid is usually produced by sulfonation of 2-naphthol with the addition of sodium sulfate at 85—105°C. This acid is also used as a coupling component in the production of a2o dyes such as Acid Black 26. 2,6-Naphthalenediol is used as a component in the manufacture of aromatic polyesters which, as is also tme of the corresponding amides, display Hquid crystal characteristics (52). 

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 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). 

Melt spinning polyesters is preferred to solution spinning because of its lower cost. Due to the hydrophobic nature of the fiber, sulfonated terephthalic acid may be used as a comonomer to provide anionic sites for cationic dyes. Small amounts of aliphatic diacids such as adipic acid may also be used to increase the dyeability of the fibers by disturbing the fiber s crystallinity. 

Although low-molar-mass aliphatic polyesters and unsaturated polyesters can be synthesized without added catalyst (see Sections 2.4.1.1.1 and 2.4.2.1), the presence of a catalyst is generally required for the preparation of high-molar-mass polyesters. Strong acids are very efficient polyesterification catalysts but also catalyze a number of side reactions at elevated temperature (>160°C), leading to polymers of inferior quality. Acid catalysts are, therefore, not much used. An exception is the bulk synthesis of hyperbranched polyesters reported in Section 2.4.5.1, which is carried out at moderate temperature (140°C) under vacuum in the presence of p-toluene sulfonic acid catalyst. The use of strongly acidic oil-soluble catalysts has also been reported for the low-temperature synthesis of polyester oligomers in water-in-oil emulsions.216... 

The ester class also comprises natural oils, such as vegetable oil [75] spent sunflower oil [940,941,992,993] and natural fats, for example, sulfonated flsh fat [161]. In water-based mud systems no harmful foams are formed from partially hydrolyzed glycerides of predominantly unsaturated Ci6 to C24 fatty acids. The partial glycerides can be used at low temperatures and are biodegradable and nontoxic [1280]. A composition for high-temperature applications is available [1818]. It is a mixture of long chain polyesters and polyamides. 

Extraction or dissolution almost invariably will cause low-MW material in a polymer to be present to some extent in the solution to be chromatographed. Solvent peaks interfere especially in trace analysis solvent impurities also may interfere. For identification or determination of residual solvents in polymers it is mandatory to use solventless methods of analysis so as not to confuse solvents in which the sample is dissolved for analysis with residual solvents in the sample. Gas chromatographic methods for the analysis of some low-boiling substances in the manufacture of polyester polymers have been reviewed [129]. The contents of residual solvents (CH2C12, CgHsCI) and monomers (bisphenol A, dichlorodiphenyl sulfone) in commercial polycarbonates and polysulfones were determined. Also residual monomers in PVAc latices were analysed by GC methods [130]. GC was also... 

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