Polyarylether sulfone

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).

Hazardous Decomp. Prods. Heated to decomp., emits acrid smoke and irritating fumes Uses Liq. crystal polymers polyarylether sulfones pharmaceuticals Manuf./Distrib. Aldrich http //www.sigma-aidrich.com-, AmeriBrom http //www.ameribrom.com, Atlanta Chem. Dead Sea Bromine http //www.dsbg.com-, Fluka http //www.sigma-aldrich. com Sigma... 

Techniques for chloromethylating polyarylether sulfones, polyphenylene oxide, phenolic resins, and model compounds were described recently [191]. When the subsequent products are cmiverted to quaternary amines, there is a decrease in the quatemization rate with increase in degree of substitutimi. This may be due to steric effects imposed by restricted rotation of the polymeric chains [191]. This phenomenon was not observed in quatemization of poly(chloromethyl styrene). The chloromethylation reaction of a polysulfone with chloromethyl ether, catalyzed by stannic chloride, can be illustrated as follows ... 

Polyethersulfone Polyarylether sulfone Tetramethyl bisphenol-A poiysuifone Poiysuifone and polysulfones with pendent groups... 

G.L. Han, Q.G. Zhang, A.M. Zhu, Q.L. Liu, Pervaporation separation of methanol/methyl tert-butyl ether mixtures using polyarylether-sulfone with cardo membranes, Sep. Purif. Technol. 107 (2013) 211-218. 

During the last 40 years, ABS blends with most polymers have been patented. For example, wdth PVC in 1951, PC (introduced in 1958) in 1960, polyamide (PA-6) a year later [Grabowski, 1961a], polysulfone (PSF) in 1964, CPE in 1965, PET in 1968, polyarylether sulfone (PAES) and styrene-maleic anhydride (SMA) in 1969 (the blend is one of two resins called high heat ABS — the other being ABS in which at least a part of styrene was replaced with p-methylstyrene), polyethersulfone (PES) in 1970, polyarylates (PAr) in 1971, polyurethane in 1976, polyarylether (PPE or PAE) in 1982, with polyphenylene sulfide (PPS) in 1991, etc. 

Polyarylether sulfones are an important group of high performance polymers the first member, Bakelite polysulfone (Udel 50), may be made by condensation of a bisphenol (as the disodium salt, 51) with 4,4 -dichlorodiphenyl sulfone 52 (Equation 6). 

Both the sulfone 52 and the disulfonyl chloride 55 may be made by reactions involving the use of chlorosulfonic acid (see Chapter 3, p 29 and Chapter 4, p 74 respectively). A polyarylether sulfone 53 can be efficiently sulfonated by treatment with sulfuric acid followed by chlorosulfonic acid. The reaction mixture was left at 25 °C for 12 hours to yield a sulfonated resin of ion-exchange capacity 0.2 mequiv. Sulfonated polysulfones, useful in reverse osmosis desalination membranes, may be prepared by sulfonation of a commercial polysulfone with chlorosulfonic acid. The polysulfone Udel PI700 can be sulfonated by chlorosulfonic acid or trimethylsilylchlorosulfonate to form proton-conducting membranes for fuel cells and supercapacitors. ... 

FIG. 5.18 Amination of chloromethylated polyarylether sulfone by a (a) moDoamine (trimethylamine) and (b) diamine (tetramethylhexane methylenediamine) [161]. 

V [161]. Park et al. [162] published a study on the preparation of solid-state alkaline electrolytes based on chloromethylated polyarylether sulfone (Fig. 5.18) via three different ways of amination (i) by using a monoamine (ii) by using a diamine and (iii) by using a mixture of monoamine and diamine. 

In the first example of the application of the homocoupling reaction of aryl chlorides to polymer synthesis, high molecular weight polyarylether sulfones were prepared by the Ni(0) catalyzed homocoupling reaction of 4,4 -bis(p-chlorophenoxy)diphenylsulfone [equations 50 (178) and 51 (779)]. 

Almost simultaneous with the report of the preparation of polyarylether sulfones, aromatic polyether ketones were prepared via the Ni(0) catalyzed polymerization of aromatic ether ketones with chloro groups at each terminus (equation 53) (181). The reaction proceeds rapidly under mild conditions. 

Fluorine containing polyarylether sulfones NMR Sequence distribution [247]... 

As a variation on the base-catalyzed nucleopbilic displacement chemistry described, polysulfones and other polyarylethers have been prepared by cuprous chloride-catalyzed polycondensation of aromatic dihydroxy compounds with aromatic dibromo compounds. The advantage of this route is that it does not require that the aromatic dibromo compound be activated by an electron-withdrawing group such as the sulfone group. Details of this polymerization method, known as the Ullmaim synthesis, have been described (8). 

Polyarylether Ketones. The aromatic polyether ketones are tme thermoplastics. Although several are commercially available, two resins in particular, poly ether ether ketone [31694-16-3] (PEEK) from ICI and poly ether ketone ketone (PEKK) from Du Pont, have received most of the attention. PEEK was first synthesized in 1981 (20) and has been well studied it is the subject of numerous papers because of its potential use in high performance aircraft. Tough, semicrystalline PEEK is prepared by the condensation of bis(4-fiuorophenyl) ketone with the potassium salt of bis(4-hydroxyphenyl) ketone in a diaryl sulfone solvent, such as diphenyl sulfone. The choice of solvent is critical other solvents, such as Hquid HE, promote the reaction but lead to premature low molecular-weight crystals, which do not exhibit sufficient toughness (21). 

Nylon, polyacetal, polycarbonates, poly(2,6-dimethyl)phenylene oxide (PPO), polyimides, polyphenylene sulfide (PPS), polyphenylene sulfones, polyaryl sulfones, polyalkylene phthalates, and polyarylether ketones (PEEK) are stiff high-melting polymers which are classified as engineering plastics. The formulas for the repeating units of some of these engineering plastics are shown in Figure 1.15. 

Stiff polymers, such as polyphenylene, nylon 66, polyphenylene sulfone, and polyarylether ketone (PEEK), have relatively high Tg values because of the presence of phenylene and sulfone or carbonyl stiffening groups in the chain. 

In earlier investigations by the authors (2,3) solid sulfonic acid resins containing polyarylether and cyano substituents, (II) and (III), respectively, were prepared and used as proton-conductive membranes, electrode electrolytes, electrode paste, and in membrane electrode assemblies. 

Features of the new, inherent, flame-resistant active polymers such as PSU (polysulfone), PES (polyether sulfone), and PAEK (polyarylether ketone) include high levels of temperature resistance and very low smoke gas densities. 

One of the most important procedures used so far for the synthesis of polyarylethers, via the formation of successive ether linkages, was described in 1967. Such a procedure involves nucleophilic aromatic substitution, i.e. the reaction of an activated halide such as dichlorodiphenyl sulfone or di-fluorobenzophenone with a bisphenate, as outlined in Equation 1. 

In order to enhance the sulfonic acidity and therefore improve the polymer proton conductivity, a different synthetic pathway has been elaborated to introduce the sulfonic acids in the ortho position to electron-withdrawing groups (sulfones, ketones). Based on a procedure widely developed by Jan-nasch et al. for the synthesis of proton exchange polyarylethers [82,83], Chen et al. [84] designed an original and interesting monomer (Fig. 9). However, the harsh experimental conditions required (BuLi, gaseous SO2) and relatively low overall yields (24.7%) should preclude the wide development of such monomers. 

Considerable attention has been devoted to the preparation of fluorine-containing polymers because of their unique properties and high temperature performance (I). Recently we reported the preparation and characterization of novel fluorine-containing polyimides and polyethers which exhibit low moisture absorption and low dielectric constants (2, 3). Fluorinated polyimides absorb 1 wt% water and have dielectric constants of about 2.8 (all dielectric constants reported in this paper were measured at 10 kHz) vtdiereas their non-fluorinated analogs absorb as much as 3 wt% water and have dielectric constants of about 3.2. Fluorinated polyarylethers, which are free of polar groups such as ketones, imides and sulfones, absorb as little as 0.1 wt% water and have dielectric constants less than 2.8. 

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