Polyarylates

The complexity of the chemical structure of heterocyclic polymers, including PPO, which are very strong, thermally stable polymers, makes the study of their thermal and thermal-oxidative degradation difficnlt. The schemes suggested for their thermal degradation are in many cases only hypothetical, however, the available experimental data make it possible to delineate the major factors determining the thermal stability of these polymers [44-46]. 

Based on data for the thermal degradation products of PPO, the following scheme is suggested [45]  

The following characteristic of the thermal degradation of PPO has been observed in its initial stages, the products form in great quantities owing to the decomposition 

It has been established [1, 44, 45] that the degradation of PPO based on phenol, o-cresol and 2,6-dimethylphenol depends on both the structure of the repeat unit and the molecular mass. The thermal degradation of these PPO under vacuum proceeds with the release of both gaseous (hydrogen, carbon monoxide, carbon dioxide, methane, methyl chloride and ethane) and non-volatile products are aromatic compounds of the type Ar-O-Ar. It has been suggested that the thermal degradation of PPO may proceed with the formation of benzyl radicals, namely  

This results in cleavage of the chain at the ester bond closest to the free radical, with formation of an O-quinomethide and a substituted phenyl radical  

The mechanism of the pyrolysis of phenol-formaldehyde novolac resins was studied in greater detail in [17]. A resin with labelled carbon in the methylene bridges was synthesized to determine from what structural elements of the resin the coke and gases are formed. 

Thermal destruction of the resin was conducted at temperatures of 550 and 800 C. An analysis of the destruction products obtained showed that most of the carbon from the methylene bridges of the resin participate in the formation of graphite (coke) and are not removed in the form of gases. 

The carbon-containing gases formed in the pyrolysis of the resin derive partially from the bridge methylene groups and partially from the decomposition of some of the aromatic rings. 

New polsmier materials based on hetero-chain polyesters of diatomic phenols — polyarylates — are of considerable interest thanks to their valuable properties high thermal stability, mechanical strength, good dielectric properties, the ability to form strong elastic films, etc. 

A large group of polyarylates based on diatomic phenols was synthesized by V. V. Korshak and S. V. Vinogradova, et al. [18, 19]. 

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Bisphenol A. One mole of acetone condenses with two moles of phenol to form bisphenol A [80-05-07] which is used mainly in the production of polycarbonate and epoxy resins. Polycarbonates (qv) are high strength plastics used widely in automotive appHcations and appHances, multilayer containers, and housing appHcations. Epoxy resins (qv) are used in fiber-reinforced larninates, for encapsulating electronic components, and in advanced composites for aircraft—aerospace and automotive appHcations. Bisphenol A is also used for the production of corrosion- and chemical-resistant polyester resins, polysulfone resins, polyetherimide resins, and polyarylate resins. 

Noncrystalline aromatic polycarbonates (qv) and polyesters (polyarylates) and alloys of polycarbonate with other thermoplastics are considered elsewhere, as are aHphatic polyesters derived from natural or biological sources such as poly(3-hydroxybutyrate), poly(glycoHde), or poly(lactide) these, too, are separately covered (see Polymers, environmentally degradable Sutures). Thermoplastic elastomers derived from poly(ester—ether) block copolymers such as PBT/PTMEG-T [82662-36-0] and known by commercial names such as Hytrel and Riteflex are included here in the section on poly(butylene terephthalate). Specific polymers are dealt with largely in order of volume, which puts PET first by virtue of its enormous market volume in bottie resin. 

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

Uses. A principal use of thionyl chloride is in the conversion of acids to acid chlorides, which are employed in many syntheses of herbicides (qv), surfactants (qv), dmgs, vitamins (qv), and dyestuffs. Possible larger-scale appHcations are in the preparation of engineering thermoplastics of the polyarylate type made from iso- and terephthaloyl chlorides, which can be made from the corresponding acids plus thionyl chloride (186) (see Engineering plastics). 

Polycarbonates. Polyarjiates are aromatic polyesters commonly prepared from aromatic dicarboxylic acids and diphenols. One of the most important polyarylates is polycarbonate, a polyester of carbonic acid. Polycarbonate composite is extensively used in the automotive industry because the resin is a tough, corrosion-resistant material. Polycarbonates (qv) can be prepared from aUphatic or aromatic materials by two routes reaction of a dihydroxy compound with phosgene accompanied by Hberation ofHCl(eq. 5) ... 

Fig. 1. Engineering resins cost vs annual volume (11) (HDT, °C) A, polyetheretherketone (288) B, polyamideimide (>270) C, polyarylether sulfone (170- >200) D, polyimide (190) E, amorphous nylons (124) F, poly(phenylene sulfide) (>260) G, polyarylates (170) H, crystalline nylons (90—220) I, polycarbonate (130) J, midrange poly(phenylene oxide) alloy (107—150) K, polyphthalate esters (180—260) and L, acetal resins (110—140).

For a part to exhibit stmctural stiffness, flexural moduH should be above 2000 N/mm (290,000 psi). Notched l2od impact values should be deterrnined at different thicknesses. Some plastics exhibit different notch sensitivities. For example, PC, 3.2 mm thick, has a notched l2od impact of 800 J/m (15 fdbf/in.) which drops to 100 J/m (1.9 fflbf/in.) at 6.4-mm thickness. On the other hand, one bisphenol A phthalate-based polyarylate resin maintains a 250-J /m (4.7-fdbf/in.) notched l2od impact at both thicknesses. Toughness depends on the stmcture of the part under consideration as well as the plastic employed to make the part. Mechanical properties, like electrical properties, ate also subject to thermal and water-content changes. 

Most polyesters (qv) are based on phthalates. They are referred to as aromatic-aHphatic or aromatic according to the copolymerized diol. Thus poly(ethylene terephthalate) [25038-59-9] (PET), poly(butyelene terephthalate) [24968-12-5] (PBT), and related polymers are termed aromatic-aHphatic polyester resins, whereas poly(bisphenol A phthalate)s are called aromatic polyester resins or polyarylates PET and PBT resins are the largest volume aromatic-aHphatic products. Other aromatic-aHphatic polyesters (65) include Eastman Kodak s Kodar resin, which is a PET resin modified with isophthalate and dimethylolcyclohexane. Polyarylate resins are lower volume specialty resins for high temperature (HDT) end uses (see HeaT-RESISTANT POLYAffiRS). 

Both PET and PBT resin serve some of the same markets as other plastics. Nylon, unsaturated polyester fiber glass, phenoHc, PC, and polyarylate resins sometimes compete for the same molded part. 

Commercial aromatic polyester resins or polyarylates are a combination of bisphenol A with isophthahe acid or terephthahe acid (79). The resins are made commercially by solution polymerization or melt transesterification (47). 

Polyarylates are sensitive to heat. Although mechanical properties are not much affected, colors darken. Properties are given in Table 8. Hydrolytic stability and resistance to organic solvents are fair. 

Polyarylates have been employed for electrical and electronic components, firefighter helmets, and appHcations requiring higher heat-deflection temperatures than PC resins. Polyarylates were first used for lighting, especially for small automotive lenses and sodium light outdoor lamps. However, the inherent yellow color and heat-induced darkening have limited appHcations. 

Although several companies have produced polyarylates, Unitika in Japan and Hoechst-Celanese are the only ones active in the marketplace. Unitika resin is marketed in the United States by Amoco Performance Polymers under the Ardel trademark. The reason for this decline may be the competition of PC, polyester carbonates, and polysulfone resins. Worldwide sales are quite small, probably less than 1000 t/yr. 

In the absence of fire retardants the material has a limiting oxygen index of 27.5 and may bum slowly. Only some grades will achieve a UL 94 V-1 rating. The Underwriters Laboratories continuous use temperature index is also somewhat low and similar to the polyarylates with ratings of 135-140°C (electrical) and 105°C (mechanical with impact). Initial marketing has emphasised comparisons with the aliphatic nylons for the reasons given in the previous... 

The polyetherimides are competitive not only with other high-performance polymers such as the polysulphones and polyketones but also with polyphenylene sulphides, polyarylates, polyamide-imides and the polycarbonates. 

In the 1980s a number of copolymers became established, known as polyester carbonates, which may be considered as being intermediate between bisphenol A polycarbonates and the polyarylates discussed in Chapter 25. 

The polyaryl ether ketones quickly became established as outstanding heat-... 

Polyaryl ether ketones may be processed on conventional injection moulding and extrusion equipment, providing sufficiently high temperatures can be achieved. Melt temperatures required are typically 370°C for unreinforced PEEK, 390°C for reinforced PEEK and both unreinforced and reinforced PEK and unreinforced PEEKK, and 410°C for reinforced PEEKK. For the latter material a temperature profile from feed zone to nozzle would be... 

Highly aromatic thermoplastic polyesters first beeame available in the 1960s but the original materials were somewhat difficult to process. These were followed in the 1970s by somewhat more processable materials, commonly referred to as polyarylates. More recently there has been considerable activity in liquid crystal polyesters, which are in interest as self-reinforeing heat-resisting engineering thermoplastics. 

With a somewhat lower level of heat resistance but with many properties that make them of interest as engineering materials alongside the polycarbonates, polysulphones, poly(phenylene sulphides) and polyketones are the so-called polyarylates which are defined as polyester from bis-phenols and dicarboxylic acids. 

One such material is the copolymer first marketed by the Japanese company Unitika in 1974 as U-Polymer and more recently by the Belgian company Solvay as Arylef and Union Carbide as Ardel. (Around 1986 the Union Carbide interest in Ardel, as well as in polysulphones, was taken over by Amoco.) Similar polyarylates have since been marketed by Hooker (Durel), Bayer (APE) and DuPont (Arylon). This is a copolyester of terephthalic acid, isophthalic acid and bis-phenol A in the ratio 1 1 2 Figure 25.23). 

Table 25.11 Principal characteristics of the polyarylate Arylef UlOO...

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

Figure 4 Tensile modulus of polyarylate-polystyrene (70 30) blend added with polyarylate-b-polystyrene (0-10) [39].

Polyarylate (PAR)-b-PSt and PAR-b-PMMA for compatibiiizers are described 135,39,40). The addition of PAR-b-PSt (1-10 parts) to 100 parts of a blend of PAR-PSt (7w-3w) resulted in improvement of the tensile and flexural modulus (Fig. 4), and PSt dispersed particles were diminished from 1-5 microns to an order that is undetectable by SEM, indicating the excellent, compatibilizing effect of the block copolymer. The alloy thus formed exert the characteristic of PAR, an engineering plastic, as well as easy processability of PSt. Addition of PAR-b-PMMA (3 or 8 parts) to 100 parts of a blend of PAR-polyvinylidenefluoride (PVDF) (7w-3w) resulted in improved microdispersed state of PVDF due to compatibility of PMMA with PVDF, while segregation of PVDF onto the surface was controlled. 

Polyarylates are highly aromatic linear polyesters with high values of (up to 194°C has been quoted) and which are self-extinguishing. 

PPO BASED POLYARYL ETHOR OLASS-RElNFOftC(D SILICONS POLYSTYRENE COPOLYMERS... 

STYRENE-ACRYLONITILE AMINOPLASTICS POLYARYL ETHER POLYARYL SULFONE... 

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