Poly aryl ether ketone

Several poly aryl ether ketones, generically given the abbreviation PAEK, have been reported in the literature, including those shown in Table 21.5. Of these, three have been in commercial production. They are ... 

It is interesting to note that all the new aromatic systems, as described, undergo displacement polymerizations in DMAC solvent by the K2CO3 method, except perfluoroalkylene [10] and amide activated polymerization [9], which were performed in NMP solvent. The displacement polymerization in DMAC solvent was carried out at 155-164°C. poly(aryl ether ketones) require less reaction time (3-6 h) than other aromatic systems for synthesis of polyethers [15]. Synthesis of the fluorinated polyether as reported by Irvin et al. [16] was carried out at room temperature for 16 h (Mw = 75,000), whereas the same polymer by Mercer et al. [17] was synthesized at 120°C for 17 h (Mw = 78,970). 

As part of an effort to develop high-performance, high-temperature-resistant polymers for microelectronics applications, we also recently described a series of both partially fluorinated and nonfluorinated poly(aryl ether ketone)s containing amide, amide-imide, cyano oxadizole, or pyridazine groups and characterized their thermal and electrical properties.11... 

Aromatic poly(aryl ether ketone)s containing 1,4-naphthalene moieties were prepared by the reaction of a bisphenol and 2 in the presence of potassium carbonate in DM Ac at 160°C as depicted in Scheme 3. A typical polymerization was carried out as follows To a 100-ml round-bottom flask was added 8.32 g (O.OlOmol) of2, 3.36g (O.OlOmol) of4,4 -(hexafluoroisopropylidene) diphenol, 51.2 g ofDMAc, and 3.1 g (0.022 mol) of potassium carbonate. The mixture was heated to 160°C with stirring under nitrogen for 18 h. The mixture was allowed to cool to room temperature. The polymer was precipitated by pouring the reaction mixture into a blender containing about 100 ml of water, filtered, washed three times with water and dried to yield 8.1 g (92% yield) as a white powder. 

Polycondensation reactions of 2 with diphenols were carried out in DMAc at 160°C using an excess of potassium carbonate to yield viscous solutions ofthe desired poly(aryl ether ketone)s. Judging by the viscosity increase, the polymerization reaction was near completion after only about 8h at 160°C. Aqueous... 

Scheme 3. synthesis of fluorinated poly (aryl ether ketone )s 3-7... 

Poly(arylether ketone), conducting, 7 524 Poly(aryl ether ketone)s, sulfonation reaction of, 23 717-718 Poly(di-n-alkylsilanes), thermochromic materials, 6 619... 

Direct copolymerization techniques have also been employed in the s)m-thesis of sulfonated poly(aryl ether ketones),i i polyimides, i 5 and poly(benzoimidazoles). The synthesis of random disulfonated biphenol poly(arylene ether sulfone) copolymers (BPSH x where x represents the percentage of disulfonated diphenylsulfone moieties in the polymer versus unsulfonated diphenylsulfone moities) (14) is shown in Scheme 3.5. 

In the sulfonated poly(arylene) systems described so far, the sulfonic acid groups have been statistically distributed along the polymer main chain. Poly(arylenes) in which the sulfonic acid sites are separated from the main chain by means of a spacer group have also been developed. Examples of systems in which this has been attempted include poly(p-phenylenes) (17),i isr poly(p-phenylene)-poly(aryl ether ketone) copolymers (18), and polyimides (19,20). These are shown in Eigure 3.24. 

Xing, P., Robertson, G. R, Guiver, M. D., Mikhailenko, S. D. and Kaliaguine, S. 2004. Sulfonated poly(aryl ether ketone)s containing the hexafluoroisopro-pylidene diphenyl moiety prepared by direct copolymerization, as proton exchange membranes for fuel cell application. Macromolecules 37 7960-7967. 

Poly(aryl ether ketone) Cone, sulfuric acid, trifluorometh-anesulfonic acid, diphenyl sulfone, sulfolane Alcohol, ether, methylene chloride... 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

Fig. 8 Chemical structures of fluorinated poly(aryl ether ketone)s...

Whereas UL 94 delivers only a classification based on a pass-and-fail system, LOI can be used to rank and compare the flammability behavior of different materials. In Figure 15.2 the increasing LOI values are presented for different polymers as an example POM = poly(oxymethylene), PEO = poly(ethyl oxide), PMMA = poly(methyl methacrylate), PE = polyethylene), PP, ABS, PS, PET = polyethylene terephthalate), PVA = poly(vinyl alcohol), PBT, PA = poly(amide), PC, PPO = poly(phenylene oxide), PSU, PEEK = poly(ether ether ketone), PAEK = poly(aryl ether ketone), PES, PBI = poly(benzimidazole), PEI = poly(ether imide), PVC = poly(vinyl chloride), PBO = poly(aryl ether benzoxazole), PTFE. The higher the LOI, the better is the intrinsic flame retardancy. Apart from rigid PVC, nearly all commodity and technical polymers are flammable. Only a few high-performance polymers are self-extinguishing. Table 15.1 shows an example of how the LOI is used in the development of flame-retarded materials. The flame retardant red phosphorus (Pred) increases... 

Acyl cations are involved as propagating species in the synthesis of poly-(ether ketone)s. Poly (ether ketone)s are a class of thermoplastic crystalline polymers that have many desirable properties that make them useful as high-performance engineering materials [153,154]. The poly(ether ke-tone)s with the most useful properties are actually para-linked poly(aryl-ether ketone)s (PAEKs). They have excellent chemical resistance to oxidation and hydrolysis, high thermal stability, and many useful mechanical properties. Unlike some other materials with similar properties they are readily melt processable using conventional equipment. In addition, their mechanical properties are not affected deleteriously by most solvents. These polymers are usually crystalline. PAEKs contain arene groups joined by ether and carbonyl linkages. For example, two commercial poly-(ether ketone)s are PEK and PEEK (Fig. 36). 

Specialty polymers achieve very high performance and find limited but critical use in aerospace composites, in electronic industries, as membranes for gas and liquid separations, as fire-retardant textile fabrics for firefighters and race-car drivers, and for biomedical applications (as sutures and surgical implants). The most important class of specialty plastics is polyimides. Other specialty polymers include polyetherimide, poly(amide-imide), polybismaleimides, ionic polymers, polyphosphazenes, poly(aryl ether ketones), polyarylates and related aromatic polyesters, and ultrahigh-molecular-weight polyethylene (Fig. 14.9). 

Ether groups are present in polymers containing other functionalities in the backbone. Among these are the a/f-polymers poly(oxy-1,4-phenylene-carbonyl-1,4-phenylene) or poly(aryl ether ketone) or poly(ether ketone) or PEK, poly(aryl ether ether ketone) or PEEK, poly(aryl ether ketone ketone) or PEKK, poly(aryl ether ketone ether ketone ketone) or PEKEKK, etc. The structures of PEK and PEEK are shown below ... 

As a final example of the use of proton NMR invoking spin diffusion to study miscibility of polymer blends, the use of CRAMPS to remove proton dipolar coupling in a blend of an aromatic poly(ether-imid) (PEI), and a poly(aryl-ether-ketone) (PEEK), with detection of the magnetization of the C in the blend under high resolution conditions is cited [51]. Here, detailed information on the chemical composition of the phases present, as inferred from high resolution NMR of C, is linked to typical sizes of domains as reflected in spin diffusion of proton magnetization. 

Figure 10.12 shows the and NMR spectra of poly(ether-imide)/ poly(aryl ether ketone) (PEI/PAEK) obtained from the chemical-shift selective Goldman-Shen experiment with (the righthand side) and without (the lefthand side) detection [108]. The signals from the aliphatic protons of PEI at 2 ppm are resolved from the aromatic protons of PEI and... 

Poly(aryl ether ketone)/aromatic thermoplastic polyimides Melt mixing of ca. 50 mg on a hot plate at T 400-455°C, between two sheets of Kapton repeated 10 times. DSC at 20°C/min Sauer et ah, 1996... 

Poly(aryl ketones) (PEEK, PEK, and PEKK) are commercial high temperature polymers offering an excellent combination of properties combined with thermoplastic behavior. Poly(aryl ether ketone) PAEK blends have been reviewed by Harris and Robeson [1989]. Miscibility with PEI (Ultem 1000 GE) and other PI containing isopropylidene bridging units was noted. Arzak et al. [1997] reviewed the performance ofPEEK/PEI blends and noted a synergistic behavior in ductility and impact strength as reported earlier. Utility of these blends as a thermoplastic matrix candidate for advanced composites has been proposed [Harris and Robeson, 1989 Davis et al., 1992]. 

Poly(aryl ether ketone)s have aromatic groups and both the ether group and the keto group are in the backbone. Figure 6.1 illustrates the basic repeating structures of this class of substances. Of course, there are several varieties of those structures shown in Figure 6.1, resulting from the use of comonomers, etc. A special related class is that of poly(ethersulfone). 

Poly(aryl ether ketones) belong to the class of engineering polymers. In early to mid-1970s, Raychem Corp. commercially introduced a poly-Caryl ether ketone) called Stilan . In this polymer, each ether and keto group is separated hy 1,4-phenylene units. In 1978, Imperial Chemical Industries PLC (ICI) commercialized a poly(aryl ether ketone) under the trademark Victrex PEEK. ... 

Liquid crystalline poly(aryl ether ketone) polyesters are then prepared by copolymerization of the ester group containing poly(aryl ether ketone) with a liquid crystalline polyester. The crystalline polyester is synthesized from phenylhydroquinone ferf-butylhydroquinone, 2-chloroterephthaloyl chloride and isophthaloyl chloride. ... 

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