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Poly(p-phenylene oxide)
View on Wikipedia| Names | |
|---|---|
| IUPAC name
Poly(oxy-2,6-dimethyl-1,4-phenylene)
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| Other names
Poly(p-phenylene ether), PPO, PPE
| |
| Identifiers | |
| ECHA InfoCard | 100.110.020 |
CompTox Dashboard (EPA)
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| Properties | |
| (C8H8O)n | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
Poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE), poly(oxy-2,6-dimethyl-1,4-phenylene), often referred to simply as polyphenylene oxide, is a high-temperature thermoplastic with the general formula (C8H8O)n. It is rarely used in its pure form due to difficulties in processing. It is mainly used as blend with polystyrene, high impact styrene-butadiene copolymer or polyamide. PPO is a registered trademark of SABIC Innovative Plastics B.V. under which various polyphenylene ether resins are sold.
History
[edit]Polyphenylene ether was discovered in 1959[1] by Allan Hay, and was commercialized by General Electric in 1960.
While it was one of the cheapest high-temperature resistant plastics, processing was difficult, while the impact and heat resistance gradually decreased with time. Mixing it with polystyrene in any ratio could compensate for the disadvantages. In the 1960s, modified PPE came into the market under the trademark Noryl.[2]
Properties
[edit]PPE is an amorphous high-performance plastic. The glass transition temperature is 215 °C, but it can be varied by mixing with polystyrene. Through modification and the incorporation of fillers such as glass fibers, the properties can be extensively modified.
Applications
[edit]
PPE blends are used for structural parts, electronics, household and automotive items that depend on high heat resistance, dimensional stability and accuracy. They are also used in medicine for sterilizable instruments made of plastic.[3] The PPE blends are characterized by hot water resistance with low water absorption, high impact strength, halogen-free fire protection and low density.
This plastic is processed by injection molding or extrusion; depending on the type, the processing temperature is 260–300 °C. The surface can be printed, hot-stamped, painted or metallized. Welds are possible by means of heating element, friction or ultrasonic welding. It can be glued with halogenated solvents or various adhesives.
This plastic is also used to produce air separation membranes for generating nitrogen.[4] The PPO is spun into a hollow fiber membrane with a porous support layer and a very thin outer skin. The permeation of oxygen occurs from inside to out across the thin outer skin with an extremely high flux. Due to the manufacturing process, the fiber has excellent dimensional stability and strength. Unlike hollow fiber membranes made from polysulfone, the aging process of the fiber is relatively quick so that air separation performance remains stable throughout the life of the membrane. PPO makes the air separation performance suitable for low temperature (35–70 °F, 2–21 °C) applications where polysulfone membranes require heated air to increase permeation.
Production from natural products
[edit]Natural phenols can be enzymatically polymerized. Laccase and peroxidase induce the polymerization of syringic acid to give a poly(1,4-phenylene oxide) bearing a carboxylic acid at one end and a phenolic hydroxyl group at the other.[5]
References
[edit]Translated from the article Polyphenylenether on the German Wikipedia.
- ^ Hay, A. S.; Blanchard, H. S.; Endres, G. F.; Eustance, J. W. (1 December 1959). "Polymerization by Oxidative Coupling". Journal of the American Chemical Society. 81 (23): 6335–6336. Bibcode:1959JAChS..81.6335H. doi:10.1021/ja01532a062. ISSN 0002-7863.
- ^ D. Alberti "Modifizierte aromatische Polyether" in Kunststoffe 10/87, S. 1001
- ^ A. Hohmann, W. Hielscher: Lexikon der Zahntechnik: Das grundlegende Werk: 12,000 Begriffe aus Zahntechnik und Zahnheilkunde in einem Band. Verlag Neuer Merkur, 1998, ISBN 978-3-929360-28-8
- ^ "Membrane Nitrogen Generators". parkern2.com.
- ^ Uyama, Hiroshi; Ikeda, Ryohei; Yaguchi, Shigeru; Kobayashi, Shiro (2001). "Enzymatic Polymerization of Natural Phenol Derivatives and Enzymatic Synthesis of Polyesters from Vinyl Esters". Polymers from Renewable Resources. ACS Symposium Series. Vol. 764. p. 113. doi:10.1021/bk-2000-0764.ch009. ISBN 0-8412-3646-1.
External links
[edit]- Douglas Robello. "Poly(phenylene oxide)". University of Rochester. Archived from the original on 2012-12-12.
- "USPTO registration of PPO".
Poly(p-phenylene oxide)
View on GrokipediaIntroduction and Chemical Structure
Molecular Composition
Poly(p-phenylene oxide) is an engineering thermoplastic polymer composed of repeating units where oxygen atoms connect 2,6-dimethyl-1,4-phenylene rings in the para position, forming a linear chain structure. The chemical formula of the repeating unit is , reflecting the aromatic backbone with two methyl substituents on each phenylene ring to sterically hinder ortho coupling and promote selective para linkage.[5] This composition imparts the polymer's characteristic rigidity and thermal stability due to the conjugated aromatic system bridged by ether linkages.[3] The primary precursor monomer for poly(p-phenylene oxide) is 2,6-xylenol, systematically named 2,6-dimethylphenol, a phenolic compound that undergoes oxidative coupling to yield the polymer chain.[6] This monomer's symmetric substitution pattern ensures the formation of the desired head-to-tail ether bonds without branching, resulting in a high-molecular-weight homopolymer.[7] Nomenclature for this polymer varies, with "polyphenylene oxide" (PPO) being a traditional common name emphasizing the oxide-like ether functionality, while "polyphenylene ether" (PPE) is more accurate and preferred in modern contexts, particularly under IUPAC guidelines as poly(oxy-2,6-dimethyl-1,4-phenylene).[8] The shift to PPE reflects a precise description of the ether linkages rather than implying a true oxide.[3] Commercial grades of poly(p-phenylene oxide) are produced with controlled molecular weights to balance processability and performance, typically featuring number-average molecular weights around 20,000 g/mol and weight-average molecular weights up to 60,000 g/mol.[9] These ranges allow for suitable melt viscosity in extrusion and molding applications while maintaining intrinsic material properties.[10]Polymer Backbone and Variants
The polymer backbone of poly(p-phenylene oxide) comprises linear chains of repeating -[O-(2,6-dimethyl-1,4-phenylene)]- units, where the oxygen atoms form ether linkages between para-substituted phenylene rings bearing methyl groups at the 2 and 6 positions, creating a rigid, extended structure that restricts chain flexibility and promotes high chain stiffness. This architecture arises from the aromatic phenylene groups, which enforce planarity and conjugation along the backbone, contributing to the polymer's inherent dimensional stability.[3] Due to the oxidative polymerization mechanism, the resulting chains exhibit an atactic configuration, characterized by irregular torsional angles around the ether linkages, which hinders close packing and results in an amorphous morphology. The 2,6-dimethyl substitution and lack of stereoregularity prevent the formation of ordered crystalline domains, distinguishing it from more symmetric aromatic polymers that can crystallize.[11] Common variants include end-capped poly(p-phenylene oxide), where reactive groups such as hydroxy or methacrylate are introduced at the chain termini to precisely control molecular weight and facilitate crosslinking or grafting in subsequent processing steps. Other substituted derivatives, such as those with 2,6-diphenyl groups, can induce partial crystallinity by enhancing intermolecular interactions, while modifications like copolymerization alter solubility and packing efficiency.[11] The degree of polymerization, typically ranging from 200 to 300 repeating units (corresponding to number-average molecular weights of 20,000–30,000 g/mol), directly impacts chain entanglement and melt viscosity, enabling processability via extrusion or molding for high-molecular-weight forms, whereas lower degrees yield telechelic oligomers with reduced viscosity suitable for solution-based applications.[11]Synthesis and Production
Oxidative Polymerization Methods
The oxidative polymerization of poly(p-phenylene oxide) (PPO) primarily involves the coupling of phenolic monomers, such as 2,6-dimethylphenol, using molecular oxygen or air as the oxidant to form diaryl ether linkages in the polymer backbone. This process, pioneered by Allan S. Hay, proceeds through a radical mechanism where the copper catalyst facilitates the generation of phenoxy radicals from the phenol substrate. These radicals then undergo selective C-O coupling at the para position, yielding a linear polymer chain while minimizing unwanted side reactions like C-C coupling or quinone formation.[12][13] The standard catalytic system employs copper-amine complexes, with copper(I) chloride (CuCl) coordinated to a bidentate amine ligand such as N,N'-di-tert-butylethylenediamine (DBEDA), which is widely used in industrial production for its high efficiency and selectivity. The amine ligand modulates the redox potential of the copper center, promoting oxygen activation and radical formation while suppressing over-oxidation. Other ligands, like N,N,N',N'-tetramethylethylenediamine (TMEDA), have been explored for specific applications, but DBEDA remains preferred for achieving high molecular weight PPO with low polydispersity.[13][14] The reaction is typically performed as a solution polymerization in toluene, with molecular oxygen bubbled through the mixture at mild temperatures of 25–40°C to control the exothermic process and ensure uniform oxygen distribution. This setup allows for high monomer conversion and intrinsic viscosities exceeding 0.5 dL/g, indicative of high molecular weight polymers suitable for engineering applications. The overall stoichiometry can be represented as: where Ar denotes the 2,6-dimethylphenyl group.[15][16] A key challenge in this polymerization is maintaining linearity and preventing branching or gelation, which can arise from uncontrolled radical coupling or catalyst deactivation leading to insoluble networks. The 2,6-substitution on the phenol inherently favors para-selectivity and reduces ortho branching, but optimal ligand selection in the copper complex is essential to fine-tune reaction kinetics, minimize diphenoquinone byproducts, and avoid gelation during scale-up. Studies on catalyst specificity have shown that sterically hindered amines like DBEDA effectively mitigate these issues by stabilizing the active copper species and promoting chain growth over cross-linking.[13][12]Production from Natural Sources
Poly(p-phenylene oxide) (PPO) can be produced from natural sources through enzymatic polymerization, leveraging oxidoreductase enzymes such as laccase and peroxidase sourced from fungi or plants to couple renewable phenolic monomers under mild aqueous conditions. These enzymes facilitate the oxidation of phenols to reactive phenoxyl radicals using molecular oxygen as the terminal electron acceptor, promoting selective C-O coupling to form the ether-linked polymer backbone. A prominent example involves the laccase-catalyzed polymerization of syringic acid, a naturally occurring methoxyphenol derived from plant lignins and found in sources like grapes and grains, yielding a bio-based PPO variant with a pendant carboxylic acid group and molecular weights exceeding 18,000 Da.[17][18] This biocatalytic route provides key advantages over conventional chemical oxidation, including operation at ambient temperatures and neutral pH, substantially lower energy requirements, and inherent sustainability from utilizing biodegradable enzymes and biomass-derived feedstocks without harsh solvents or toxic byproducts.[18][19] Peroxidases, often from plant sources like horseradish, can similarly drive the process by generating radicals in the presence of hydrogen peroxide, though laccases are preferred for their oxygen-dependent mechanism that avoids peroxide addition.[20] Beyond syringic acid, laccase-mediated polymerization has been applied to other natural phenols, such as vanillin from vanilla beans or lignin depolymerization and eugenol derivatives from essential oils like clove, producing PPO analogs with tailored substituents for enhanced biocompatibility.[18][21] These bio-PPO variants exhibit similar thermal stability to synthetic counterparts but with added functional groups from the monomers, enabling applications in eco-friendly composites. Enzymatic yields are generally lower than those of synthetic oxidative methods, often requiring post-reaction purification via techniques like solvent precipitation, dialysis, or chromatography to isolate high-purity polymers free from unreacted monomers or oligomeric impurities.[17][22] In the 2010s, advancements emphasized scalable biocatalysis, including optimized laccase systems for methoxyphenol polymerization in buffered media and the synthesis of heteropolymers from phenol mixtures, paving the way for industrial green production of bio-PPO with improved process economics and reduced environmental footprint.[22][21]Physical and Chemical Properties
Thermal and Mechanical Characteristics
Poly(p-phenylene oxide), often abbreviated as PPO, exhibits exceptional thermal properties due to its amorphous structure, which contributes to its high heat resistance without a distinct melting point. The glass transition temperature (T_g) of unfilled PPO is approximately 210 °C, heat deflection temperature of 192–194 °C at 1.8 MPa load, allowing for continuous service temperatures up to 120–150 °C depending on load conditions in demanding environments.[23][24][3] PPO demonstrates strong thermal stability, with thermal decomposition typically occurring above 400 °C under inert conditions, making it suitable for applications requiring prolonged exposure to elevated temperatures.[25] Additionally, its low coefficient of linear thermal expansion, ranging from 50 to 70 × 10⁻⁶/°C, ensures dimensional stability across temperature fluctuations.[26] Mechanically, unfilled PPO offers a balance of strength and toughness, with tensile strength typically between 60 and 70 MPa and elongation at break of 25 to 30%, providing good ductility for an engineering thermoplastic.[27] Its impact resistance is notable, with notched Izod values of 200 to 270 J/m, which supports its use in components subject to moderate dynamic loads.[27] The material's flexural modulus is around 2.5 GPa, reflecting inherent stiffness without reinforcement.[26] Reinforcement with glass fibers significantly enhances PPO's mechanical performance, particularly stiffness, while maintaining thermal advantages. For instance, 30% glass fiber-filled PPO achieves a flexural modulus of 7.6 GPa, a substantial increase over the unfilled variant, enabling applications demanding higher load-bearing capacity.[28] This modification also boosts tensile strength to approximately 90-130 MPa, though it reduces elongation and impact strength compared to the base resin.[29] The following table compares key thermal and mechanical properties of unfilled and 30% glass fiber-reinforced PPO:| Property | Unfilled PPO | 30% Glass Fiber-Reinforced PPO |
|---|---|---|
| Glass Transition Temperature (T_g, °C) | 210 | 210 |
| Coefficient of Thermal Expansion (×10⁻⁶/°C) | 50–70 | 20–30 |
| Decomposition Temperature (°C) | >400 | >400 |
| Tensile Strength (MPa) | 60–70 | 90–130 |
| Elongation at Break (%) | 25–30 | 2–5 |
| Notched Izod Impact (J/m) | 200–270 | 80–120 |
| Flexural Modulus (GPa) | 2.5 | 7.6 |
