Poly Phenylene Oxide

Polyphenylene oxide (PPO) is produced by the condensation of 2,6-dimethylphenol. The reaction occurs by passing oxygen in the phenol solution in presence of CU2CI2 and pyridine  

PPO is an engineering thermoplastic with excellent properties. To improve its mechanical properties and dimensional stability, PPO can he blended with polystyrene and glass fiber. Articles made from PPO could be used up to 330°C it is mainly used in items that require higher temperatures such as laboratory equipment, valves, and fittings. 

Poly(phenylene oxide) is produced by oxidative coupling of 2,6-disubstituted phenols (for example, Ar = 2,6-dimethylphenyl)  

If the R substituents are too electronegative (nitro or methoxy groups) or too bulky (r-butyl), then the coupling does not occur quinones are produced instead  

Copper (I) salts act as catalysts in the form of their complex with primary, secondary, or tertiary amines. Primary and secondary aliphatic amines must be used at low temperatures, since otherwise they are oxidized. Primary aromatic amines are oxidized to azo compounds, and secondary aromatic compounds probably to hydrazo compounds. Pyridine is very suitable. 

A product with two methyl substituents, with M = 30,000, is commercially available as poly(phenylene oxide). It has better dimensional stability than polycarbonates, acetal resins, and nylon, resists creep, and can be subjected to temperatures up to 175°C (sterilization ). 

Poly(phenylene oxides) or poly(phenyl ethers) can also be produced as insoluble compounds when cross-linking is induced by the action of light on p-hydroxyazobenzenes  

Aycock, V. Abolins and D. White. Poly(Phenylene Oxides) in J. I. Kroschwitz, editor-in-chief. Encyclopedia of Polymer Science and Engineering, 2nd ed. New York Wiley-Interscience, Vol. 13, pp. 1-30,1986. 

Wiliard Hallam Jr. Bonner, Aromatic polyketones and preparation phereof. US Patent 3065205. November 20,1962. 

Fontanille, Y. Gnanou, Chimie et physico-chimie des polymeres, 2 edition. Sciences Sup, Paris, Dunod, 2010. 

La polymirisation, Principes et applications, Paris, Polytechnica, 1994. 

Radusch, Polyfbutylene terephthalate), in Handbook of Thermoplastic Polymers Homopolymers, Copolymers, Blends, and Composites (ed. S. Fakirov), Wiley-VCH Verlag GmbH, Weinheim, Germany, Ch. 8, p. 389-419, 2002. 

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The polymer described in the last problem is commercially called poly (phenylene oxide), which is not a proper name for a molecule with this structure. Propose a more correct name. Use the results of the last problem to criticize or defend the following proposition The experimental data for dimer polymerization can be understood if it is assumed that one molecule of water and one molecule of monomer may split out in the condensation step. Steps involving incorporation of the monomer itself (with only water split out) also occur. 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

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

Polymer Blends. Commercial blends of nylon with other polymers have also been produced in order to obtain a balance of the properties of the two materials or to reduce moisture uptake. Blends of nylon-6,6 with poly(phenylene oxide) have been most successflil, but blends of nylon-6,6 and nylon-6 with polypropylene have also been introduced. 

One class of aromatic polyethers consists of polymers with only aromatic rings and ether linkages ia the backbone poly(phenylene oxide)s are examples and are the principal emphasis of this article. A second type contains a wide variety of other functional groups ia the backbone, ia addition to the aromatic units and ether linkages. Many of these polymers are covered ia other articles, based on the other fiinctionahty (see Polymers containing sulfur, POLYSULFONES). 

Many newer poly(phenylene oxide)s have been reported ia the early 1990s. Eor example, a number of poly(2,6-diphenyl-l,4-phenylene oxide)s were prepared with substituents ia the 4-positions of the pendent phenyl groups. Of particular iaterest is the 4-fluoro substitueat, which imparts a lower melting poiat, enhanced solubiUty, and a lesser tendency to crystallize than has been found for the parent material (1). 

Table 1. Thermal Properties of Poly(Phenylene Oxides)s...

The backbone of poly(phenylene oxide)s is cleaved under certain extreme reaction conditions. Lithium biphenyl reduces DMPPO to low molecular weight products in the dimer and trimer molecular weight range (20) and converts poly(2,6-diphenyl-l,4-phenylene oxide) to 3,5-diphenylphenol in 85% yield (21) (eq. 4). 

Poly(phenylene oxide)s undergo many substitution reactions (25). Reactions involving the aromatic rings and the methyl groups of DMPPO include bromination (26), displacement of the resultant bromine with phosphoms or amines (27), lithiation (28), and maleic anhydride grafting (29). Additional reactions at the open 3-position on the ring include nitration, alkylation (30), and amidation with isocyanates (31). 

The selectivity of the oxidation of 2,6-disubstituted phenols depends on the type of oxidizing agent. For example, with a series of cobalt-containing catalysts of the salcomine type, oxidation of 2,6-dimethylphenol produces three products the poly(phenylene oxide), the diphenoquinone, and... 

Halogen Displacement. Poly(phenylene oxide)s can also be prepared from 4-halo-2,6-disubstituted phenols by displacement of the halogen to form the ether linkage (48). A trace of an oxidizing agent or free radical initiates the displacement reaction. With 4-bromo-2,6-dimethylphenol, the reaction can be represented as in equation 10 ... 

Halophenols without 2,6-disubstitution do not polymerize under oxidative displacement conditions. Oxidative side reactions at the ortho position may consume the initiator or intermpt the propagation step of the chain process. To prepare poly(phenylene oxide)s from unsubstituted 4-halophenols, it is necessary to employ the more drastic conditions of the Ullmaim ether synthesis. A cuprous chloride—pyridine complex in 1,4-dimethoxybenzene at 200°C converts the sodium salt of 4-bromophenol to poly(phenylene oxide) (1) ... 

Fig. 2. Glass-transition temperature, T, for two commercially available, miscible blend systems (a) poly(phenylene oxide) (PPO) and polystyrene (PS) (42) ...

The oxidative coupling of 2,6-dimethylphenol to yield poly(phenylene oxide) represents 90—95% of the consumption of 2,6-dimethylphenol (68). The oxidation with air is catalyzed by a copper—amine complex. The poly(phenylene oxide) derived from 2,6-dimethylphenol is blended with other polymers, primarily high impact polystyrene, and the resulting alloy is widely used in housings for business machines, electronic equipment and in the manufacture of automobiles (see Polyethers, aromatic). A minor use of 2,6-dimethylphenol involves its oxidative coupling to... 

Poly(phenylene ether). The only commercially available thermoplastic poly(phenylene oxide) PPO is the polyether poly(2,6-dimethylphenol-l,4-phenylene ether) [24938-67-8]. PPO is prepared by the oxidative coupling of 2,6-dimethylphenol with a copper amine catalyst (25). Usually PPO is blended with other polymers such as polystyrene (see PoLYETPiERS, Aromatic). However, thermoplastic composites containing randomly oriented glass fibers are available. 

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).

Alloys and blends are of great commercial significance. The archetype of "alloys" is the poly(phenylene oxide)—polystyrene resin discussed eadier. Important examples of blends based on immiscible resins are afforded by the polycarbonate—poly(butylene terephthalate) resins and polycarbonate—ABS blends. 

Engineering resins can be combined with either other engineering resins or commodity resins. Some commercially successhil blends of engineering resins with other engineering resins include poly(butylene terephthalate)—poly(ethylene terephthalate), polycarbonate—poly(butylene terephthalate), polycarbonate—poly(ethylene terephthalate), polysulfone—poly (ethylene terephthalate), and poly(phenylene oxide)—nylon. Commercial blends of engineering resins with other resins include modified poly(butylene terephthalate), polycarbonate—ABS, polycarbonate—styrene maleic anhydride, poly(phenylene oxide)—polystyrene, and nylon—polyethylene. 

The forecasts made in 1985 (77) of 8—8.5% worldwide aimual growth have not materialized. The 2 x lOg + /yr engineering plastic production reported for 1985—1986 has remained fairly constant. Whereas some resins such as PET, nylon-6, and nylon-6,6 have continued to experience growth, other resins such as poly(phenylene oxide) have experienced downturns. This is due to successhil inroads from traditional materials (wood, glass, ceramics, and metals) which are experiencing a rebound in appHcations driven by new technology and antiplastics environmental concerns. Also, recycling is likely to impact production of all plastics. 

Blends of ABS with polycarbonates have been available for several years (e.g. Bayblend by Bayer and Cycoloy by Borg-Wamer). In many respects these polymers have properties intermediate to the parent plastics materials with heat distortion temperatures up to 130°C. They also show good impact strength, particularly at low temperatures. Self-extinguishing and flame retarding grades have been made available. The materials thus provide possible alternatives to modified poly(phenylene oxides) of the Noryl type described in Chapter 21. (See also sections 16.16 and 20.8.)... 

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