Aryl ether ketone copolymers

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. 

Y. M. Niu, X. L. Zhu, L. Z. Liu, Y. Zhao, G. B. Wang, and Z. H. Jiang. Synthesis and properties of poly(aryl ether ketone) copolymers with triflu-oromethyl-substituted benzene in the side chain. J. Macromol. ScL, Pure Appl. C/zem., 43(9) 1459-1467, September 2006. 

K. J. Dahl, V. Jansons, and S. Moore. Aryl ether ketone copolymers. US Patent 4 808 693, assigned to Raychem Corporation (Menlo Park, CA), February 28, 1989. 

Wang G, Geng Z, Zhu X, Zhang S, Liu X. Synthesis and characterization of soluble low-poly (aryl ether ketone) copolymers with pendent adamantyl groups. High Perform Polym 2010 22(7) 779-98. 

Havens and Reimer have used carbon-13 NMR measurements to study the sequence distribution in a series of aryl ether ketone copolymers [41]. These copolymers were based on terephthaloyl chloride (T), 1,4-diphenoxy-benzene (B), and diphenyl ether (E) and were prepared by a Friedel-Crafts reaction using either HF/BF3 or buffered AICI3 as the catalyst. The copolymers formed are comprised of T units alternating with either E or B units. 

Scheme 2.27 Structures of sulfonated poly(aryl ether ketone) copolymers (a) SPAEK-6F [135] (b) SPAEK-6F [136].

Guo et al. [180] prepared a series of sulfonated poly(aryl ether ketone) copolymers (Br-SPAEKs) by nucleophilic aromatic substitution reaction based on (6F-BPA, A2 monomer), 4,4 -DFBP, unsulfonated B2 monomer), 3,3 -disodiumsulfonyl-4,4-difluoro-benzophenone (SDFBP, sulfonated B2 monomer), and 2,4, 6-trifluoro-benzophenone (TFBP, branched... 

P. Xing, G.P. Robertson, M.D. Guiver, S.D. Mikhailenko, S. Kaliaguine, Synthesis and characterization of poly(aryl ether ketone) copolymers containing (hexafluoroiso-propylidene)-diphenol moiety as proton exchange membrane materials. Polymer 46 (10) (2005)3257-3263. 

W. Guo, X. Li, H. Wang, J. Pang, G. Wang, Z. Jiang, S. Zhang, Synthesis of branched sulfonated poly(aryl ether ketone) copolymers and their proton exchange membrane properties, J. Memb. Sci. 444 (2013) 259-267. 

Synthesis and Characterization of Poly (aryl ether ketone) Copolymers... 

In this chapter, two general synthetic methods of poly (aryl ether ketone) copolymers were introduced, that is, (1) nucleophilic substitution step copolycondensation of at least two different monomers of bisphenol and at least one dihalobenzoid compound or at least one monomer of bisphenol and at least two different dihalobenzoid compounds (2) electrophilic Friedel-Crafts copolycondensation of at least two different monomer of diphenyl ether and terephthaloyl chloride or at least one monomer of diphenyl ether and terephthaloyl chloride as well as isophthaloyl chloride. Some representative monomers were included. By the method (1), the synthesis and characterization of structural poly (aryl ether ketone) copolymers—poly (ether ether ketone)-poly (ether ether ketone ketone) (PEEK-PEEKK), poly (ether ether ketone)-poly (ether biphenyl ether ketone) (PEEK-PEDEK), poly (ether ether ketone ketone)-poly (ether biphenyl ether ketone ketone) (PEEKK-PEDEKK), poly (ether ether ketone)-poly (ether ether ketone biphenyl ketone) (PEEK-PEEKDK) and poly (ether biphenyl ether ketone)-poly (ether biphenyl ether ketone biphenyl ketone) (PEDEK-PEDEKDK) were discussed. The s5mthesis and characterization of the functional PAEK copolymers, such as liquid crystal poly (aryl ether ketone) copol5oners, poly (aryl ether ketone) copolymers with pendent group of low dielectric constant and poly (aryl ether ketone) copolymers with crosslinking moieties were also discussed in details. These PAEK copolymers showed a lot of special performance and can maybe be applied in optical waveguides, microelectronics, display devices, membrane materials and so on. 

Keywords High performance pol)rmer, poly (aryl ether ketone), copolymers, synthesis, characterization... 

In general, PAEK copolymers have been s)mthesized by two methods (1) nucleophilic substitution step copolycondensation of at least two different monomers of bisphenol and at least one dihalobenzoid compound or at least one monomer of bisphenol and at least two different dihalobenzoid compounds (2) electrophilic Fiiedel-Crafts copolycondensation of at least two different monomer of diphenyl ether and terephthaloyl chloride or at least one monomer of diphenyl ether and terephthaloyl chloride as well as isophthaloyl chloride. Some of bisfluoro, bisphenol monomers, aromatic bisbenzoyl chloride and diphenyl ether used for the synthesis of poly (aryl ether ketone) copolymers have been included in Table 10.1. 

The synthesis and characterization of the novel poly (aryl ether ketone) copolymers with liquid crystallinity... 

A series of novel thermotropic liquid crystalline poly (aryl ether ketone) copolymers were synthesized by the reaction of 4,4 -biphenol (BP) and substituted hydroquinone with 4,4 -difluorobenzophenone according to Scheme 10.7 [39]. The synthesis procedure of copolymers is like that of reference [43]. 

Novel poly(aryl ether ketone) copolymers with pendant 3-(tri-fluoromethyl)phenyl groups (FPAEKs) were S5mthesized by the reaction of a crystal-disrupting monomer, 3-(trifluoromethyl)phen-ylhydroquinone (FH) and a mesogenic monomer, 4,4-biphenol (BP) with l,4-bis(p-fluorobenzoyl)benzene (BF). The synthetic routes of FPAEKs are shown in Scheme 10.8. 

A new monomer (4-(4 -trifluoromethyl)phenoxyphenyl)hydro-quinone (TFPOPH) was synthesized in a three-step synthesis. A series of poly (aryl ether ketone) copolymers were prepared by the reaction of (4-(4 -trifluoromethyl)phenoxyphenyl) hydroquinone and hydroquinone (HQ) with 4,4 -difluorobenzophenone (Dre) in the presence of potassium carbonate. A typical polymerization was carried out as follows To a three-neck round bottom flask were added hydroquinone and (4-(4 -trifluoromethyl)-phenox)q henyl) hydroquinone (TFPOPH) (total O.lOmol) in molar ratios of 100 0, 80 20, 60 40, 40 60, 20 80 and 0 100, 4,4 -difluorobenzophenone (DFB), toluene and 3.04 g (0.022 mol) of potassium carbonate and tetramethylene sulfone (TMS) (a prescribed amount shown in Table 10.5) and heated to 140°C to remove produced water by azeotropic distillation with toluene and then rose up to 210°C for 4-6 h. The copolymer was precipitated by pouring the hot reaction mixture into a large amount of distilled water, filtered, and washed... 

Synthesis of Foly(aryl ether ketone) Copolymers Containing Adamantyl-substituted Naphthalene Rings... 

Poly (aryl ether ketone) copolymers having various compositions of 2.7-dihydroxynaphthalene and HQ were synthesized by the nucleophilic substitution reaction of 4,4 -difluorobenzophenone (DFB) with HQ and DHN in the presence of sodium carbonate and potassium carbonate (Scheme 10.13). 

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