Aromatic poly sulfonates

Sinclair-Koppers Co. Lexan 125 bisphenol A polycarbonate from General Electric Co. Polysulfone aromatic poly(sulfone-ether) from Union Carbide Corp. and PPO poly(2,6-dimethyl-p-phenylene oxide) from General Electric Co. 

Bis-(4-chlorophenyl)-sulfone is an important intermediate, which is used mainly for the preparation of aromatic poly(sulfone)s and for the synthesis of bis-(aminophenyl)-sulfone. This compound is required both for the therapy of leprosy and for curing epoxy resins. 

Nucleophilic displacement chemistry involving aromatic dihalides and bisphenois, represented the first means by which high molecular weight aromatic polyethers could be produced. This technology has since been the basis for all commercial processes developed for this family of Engineering Polymers. The preparative method involves the nucleophilic polycondensation of a bispheno salt with an activated aromatic dihalide in an aprotic solvent. Further investigations have shown that the method has a very wide scope and that it can be applied to the preparation of a host of aromatic poly (sulfone ethers), poly (ketone ethers) and other related polyethers. 

The aromatic poly(benzothiazole) from 15 and 29 is almost amorphous and easily soluble in strong acids such as concentrated sulfuric acid and methane-sulfonic acid.26 It also dissolves in organic solvents such as HMPA and o-chlorophenol. The increased solubility and amorphous nature of this polymer is also ascribed to reduced intermolecular forces and to looser packing owing to the presence of highly distorted diphenylhexafluoroisopropylidene units in the polymer backbone. 

Radiation-Resistant, Amorphous, All-Aromatic Poly (ary lene ether sulfones)... 

This paper reviews some of our work on general methods for the synthesis of polyaromatics containing either terminal or pendant styrene groups and their thermal polymerization. The examples provided in this paper refer to an aromatic polyether sulfone (PSU) and poly-(2,6-dimethy1-1,4-phenylene oxide) (PPO). 

An example for the synthesis of poly(2,6-dimethyl-l,4-phenylene oxide) - aromatic poly(ether-sulfone) - poly(2,6-dimethyl-1,4-pheny-lene oxide) ABA triblock copolymer is presented in Scheme 6. Quantitative etherification of the two polymer chain ends has been accomplished under mild reaction conditions detailed elsewhere(11). Figure 4 presents the 200 MHz Ir-NMR spectra of the co-(2,6-dimethyl-phenol) poly(2,6-dimethyl-l,4-phenylene oxide), of the 01, w-di(chloroally) aromatic polyether sulfone and of the obtained ABA triblock copolymers as convincing evidence for the quantitative reaction of the parent pol3rmers chain ends. Additional evidence for the very clean synthetic procedure comes from the gel permeation chromatograms of the two starting oligomers and of the obtained ABA triblock copolymer presented in Figure 5. 

Colquhoum, H. M. Lewis, D. E Ben-Haida, A. Hodge, P. Ring-chain interconversion in high-performance polymer system. 2. Ring-opening polmerization-copolyetherification in the synthesis of aromatic poly(ether sulfones). Macromolecules 2003, 36, 3775-3778. 

Gil, M., Ji, X., Li, X., Na, H., Hampsay, J., Lu, Y. (2004). Direct synthesis of sulfonated aromatic poly(ether ether ketone) proton exchange membranes for fuel cell applications. /. Membrane Sci. 234, 75-81. 

Figure 5.11 SEM photographs of the surface texture of composite polyamide membranes from aliphatic and aromatic amines (a) uncoated microporous poly-sulfone (b) polyamide from polyethylenimine and trimesoyl chloride (c) tri-ethylenetetramine and trimesoyl chloride (d) 1,3-benzenediamine and trimesoyl chloride (e) 2,4-toluenediamine and trimesoyl chloride (f) 4-methoxy-1,3-benzenediamine and trimesoyl chloride. Note the smooth surface for aliphatic amine-based interfacial trimesamides and the coarse ridge-and-valley structure for aromatic amine-based interfacial trimesamides.

Noshay and Robeson27 reviewed the extensive patent literature on poly(sulfonated aromatics) and their industrial applications. They carried out the sulfonation of a bisphenol-diphenyl sulfone polycondensate by means of a 2 1 S03/TEP complex38 in... 

Poly(biphenyl ether sulfone)s can be prepared, with carbonates or with the alkali metal hydroxides as activators. In the carbonate method, the poly(sulfone)s are prepared by the reaction of equimolar amounts of dihydroxy aromatic compounds and dihalodiaryl sulfones. Dihydroxy aromatic compounds are BP, 4,4 -dihydroxydiphenyl sulfone, hydroquinone, bisphenol A. Dihalodiaryl sulfones, are 4,4 -dichlorodiphenyl sulfone or 4,4 -difluorodiphenyl sulfone. 0.5 to about 1.0 mole of an alkali metal carbonate per mole of hydroxyl group is added. The condensation is conducted as azeotropic condensation, at a temperature of 210-300°C up to 15 hours. 

The actual formation of hyperbranched material proceeds during the polymerization of 3,5-difluoro-4 -hydroxydiphenyl sulfone in the presence of 3,4,5-trifluorophenylsulfonyl benzene or tris(3,4,5-trifluorophenyl)phos-phine oxide as a core molecule. Cyclic oUgomers formed dining this polymerization contribute to a low-molecular-weight polymer ranging from 3400 to 8400 Dalton. A triazin-based AB2 monomer has also been described. This monomer is shown in Figure 7.8. A hyperbranched aromatic poly(ether sulfone) with sulfonyl chloride terminal groups has been prepared by the polycondensation of 4,4 -(m-phenylenedioxy)-bis-(benz-enesulfonyl chloride). The polymerization was carried out in nitrobenzene at 120°C for 3 h in the presence of a catalytic amount of FeCls. ... 

K. Matsumoto and M. Ueda. Synthesis of hyperbranched aromatic poly-(ether sulfone) with sulfonyl chloride terminal groups. Chem. Lett., 35 1196-1197,2006. 

B. Liu, G.P. Robertson, D.-S. Kim, M.D. Guiver, W. Hu, Z. Jiang, Aromatic poly(ether ketone)s with pendant sulfonic acid phenyl groups prepared by a mild sulfonation method for proton exchange membranes. Macromolecules 2007, 40(6), 1934-1944. 

S. Matsumura, A.R. Hlil, C. Lepiller, J. Gaudet, D. Guay, A.S. Hay, lonomers for proton exchange membrane fuel cells with sulfonic acid groups on the end groups Novel linear aromatic poly(sulfide-ketone)s. Macromolecules 2007, 41(2), 277-280. 

Dimethyl sulfate alkylates almost quantitatively sterically hindered aromatic poly(pyridine ether)s and poly(pyridine ether sulfone)s in nitrobenzene. The reaction can be illustrated as follows ... 

Wang et al. [32] sulfonated bisphenol based wholly on aromatic poly(arylene ether sulfone) (PBPS) at various degrees of sulfonation. The surfaces of the membranes prepared from these polymers were studied by AFM. Figure 8.12 shows AFM... 

ES404, an aromatic poly(ether sulfone) membrane of nominal MWCO (4000 Da)... 

The most promising heat-resistant plastics for hard challenges are poly-sulfones. Today, the widely used aromatic polysulfones as constmctional... 

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