4,4 -Dichlorodiphenyl sulfone

An alternative synthesis route for PES involves the partial hydrolysis of dichlorodiphenyl sulfone (2) with base to produce 4-chloro-4 -hydroxydiphenylsulfone [7402-67-7] (3) followed by the polycondensation of this difimctional monomer in the presence of potassium hydroxide or potassium carbonate (7). 

It is prepared from the polycondensation of the disodium salt of bisphenol A and 4,4-dichlorodiphenyl sulfone in a polar aprotic solvent such as dimethyl sulfoxide (26). 

The resins are made by batch processes employing Friedel-Crafts reactions or nucleophilic aromatic substitution. Udel resin and Radel R resin are produced by the nucleophilic displacement of chloride on 4,4 -dichlorodiphenyl sulfone by the potassium salts of bisphenol A and 4,4 -biphenol, respectively (97) ... 

Polyether sulfones can be prepared by the reaction of the sodium or potassium salt of bisphenol A and 4,4-dichlorodiphenyl sulfone. Bisphenol A acts as a nucleophile in the presence of the deactivated aromatic ring of the dichlorophenylsulfone. The reaction may also be catalyzed with Friedel-Crafts catalysts the dichlorophenyl sulfone acts as an electrophile ... 

When 4,4 -dichlorodiphenyl sulfone is treated with two equivalents of sodium hydroxide in aqueous DMSO, only one Cl is hydrolyzed229. Presumably the arylsulfonyl activating effect is eliminated by conjugation of O with the ring in the first hydrolysis product. 

The SnAt reactions were first successfully used in the synthesis of high-molecular-weight poly(arylene etherjs by Johnson et al.4,5 This reaction represents a good example for poly(ether sulfonejs in general, either in laboratory -or industrial-scale preparations. In this procedure, the bisphenol A and sodium hydroxide with an exact mole ratio of 1 2 were dissolved into dimethyl sulfoxide (DMSO)-chlorobenzene. The bisphenol A was converted into disodium bisphenolate A, and water was removed by azeotropic distillation. After the formation of the anhydrous disodium bisphenolate A, an equal molar amount of 4,4,-dichlorodiphenyl sulfone (DCDPS) was added in chlorobenzene under anhydrous conditions and the temperature was increased to 160°C for over 1 h... 

Extraction or dissolution almost invariably will cause low-MW material in a polymer to be present to some extent in the solution to be chromatographed. Solvent peaks interfere especially in trace analysis solvent impurities also may interfere. For identification or determination of residual solvents in polymers it is mandatory to use solventless methods of analysis so as not to confuse solvents in which the sample is dissolved for analysis with residual solvents in the sample. Gas chromatographic methods for the analysis of some low-boiling substances in the manufacture of polyester polymers have been reviewed [129]. The contents of residual solvents (CH2C12, CgHsCI) and monomers (bisphenol A, dichlorodiphenyl sulfone) in commercial polycarbonates and polysulfones were determined. Also residual monomers in PVAc latices were analysed by GC methods [130]. GC was also... 

The most interesting aminomethyl derivative of condensation polymers that we have prepared to date Is derived from direct reduction of poly(2-cyano-l,3-phenylene arylene ether), 20. Enchainment of benzonitrile repeat units Is accomplished by coupling 2,6-dichlorobenzonitrile with the potassium salt of bisphenol-A copolymers with lower nitrile contents can be produced by copolycondensation of bisphenol-A, 2,6-dichlorobenzonitrile and 4,4 -dichlorodiphenyl sulfone.21 The pendent nitrile function provides an active site for further elaboration. 

An aromatic polysulfone based on 4,4 -biphenol and 4,4 -dichlorodiphenyl sulfone (Bp PSF) was shown to be the most resistant of a systggatic series of poly (arylene ether sulfones) to Co gamma irradiation. 

The reaction sequence used to synthesize these flexible systems involved four steps which are outlined in Figure 1. The first of these was an aromatic nucleophilic substitution, a polymer forming reaction in which 4,4 -dichlorodiphenyl sulfone reacts with various diols. The second step, an Ullmann ether reaction, gives bromine terminated products in which the bromines can be replaced by ethynyl end groups in the final stages. 

Monomer/Oligomer Synthesis. The first two steps in the four step reaction sequence of Figure 1 are capable of producing both monomer and oligomer. The first step, aromatic nucleophilic substitution, is a polymer forming reaction under the correct stoichiometric conditions. In order to favor the formation of monomer with a small amount of oligomer, the substitution was carried out at a 4 1 ratio of diol to dichlorodiphenyl sulfone. This led to a predominantly monomeric product (IV) with only the requirement that the excess diol be removed from the product to eliminate the potential presence of low molecular weight species in later reactions. 

These polymers show lower water uptake than the analogous sulfonated poly(arylene ether sulfone) materials, possibly suggesting some interaction between the aromatic nitrile and sulfonic acid. The phosphine oxide functional moiety could also be used as a compatibilizer with other materials. Sulfonated poly(arylene ether phosphine oxide sulfone) terpoly-mers have been prepared both with sulfonated triphenyl phosphine oxide and with triphenyl phosphine oxide with 3,3 -disulfonate-4,4 —dichlorodiphenyl sulfone as the sulfonic acid bearing monomer. Block copolymers containing phosphine oxide appear to avoid the ether—ether interchange that results when non—phosphine oxide blocks are utilized, and this is being further pursued. ... 

Mulhaupt et al. synthesized novel soluble copoly-arylenes via a Ni(0)-catalyzed coupling reaction of aryl chlorides. Molar ratios of dichlorodiphenyl sulfone (a) to m-dichlorobenzene (y) were used to vary the amount of m-phenylene in the final copolymer. Then these copolymers were dissolved in chloroform and sulfonated with chlorosulfonic acid. The synthe-... 

Cho et al. have recently described the synthesis of a sulfonimide containing monomer and the resulting poly (ary lene ether sulfone) copolymers. In this procedure 3,3 -disulfonate-4,4 —dichlorodiphenyl sulfone was refluxed in thionyl chloride, isolated, and then reacted with trifluoromethanesulfonamide in the presence of triethylamine to form the sulfonamide analogue monomer as shown in Figure 44. This... 

The technically most important poly(arylene ether sulfone) is obtained from bisphenol A and 4,4 -dichlorodiphenyl sulfone by nucleophilic aromatic polysubstitution. 

Synthesis of Poly(arylene Ether Sulfone) from Bisphenol A and 4,4 - Dichlorodiphenyl Sulfone... 

Arylene ether/imide copolymers were prepared by the reaction of various amounts 4,4 -carbonylbis[Ar-(4 -hydroxyphenyl)phthalimide] and 4,4 -biphenoi with a stoichiometric portion of 4,4 -dichlorodiphenyl sulfone in the presence of potassium carbonate in NMP/CHP [55]. To obtain high molecular weight polymer, the temperature of the reaction was kept below 155 °C for several hours before heating to >155°C in an attempt to avoid undesirable side reactions such as opening of the imide ring. The imide ring is not stable to conditions of normal aromatic nucleophilic polymerizations unless extreme care is exercised to remove water. Special conditions must be used to avoid hydrolysis of the imide as previously mentioned in the section on Other PAE Containing Heterocyclic Units and as practiced in the synthesis of Ultem mentioned in the Historical Perspective section. 

The first aromatic sulfone polymer produced commercially was introduced as Bakelite polysulfone but now is sold by Union Carbide under the trade name Udel. It is made by reaction of the disodium salt of bisphenol A (BPA) with 4,4 -dichlorodiphenyl sulfone in a mixed solvent of chlorobenzene and dimethyl sulfoxide (eq. 12). 

High molecular weight polymers have been recently prepared by condensation of alkali metal salts of biphenols with activated halides such as 4.4 -dichlorodiphenyl sulfone 50). The polymer (II) prepared from 4.4 -isopropylidenediphenol and 4.4 -dichlorodiphenylsulfone is now commercially available. 

To a 250 ml flask equipped with a stirrer, a thermometer, a water condenser and Dean-Stark trap was added 11.42 g of 4.4 -isopropylidenediphenol (0.05 moles), 13.1 g of a 42.8% potassium hydroxide solution (0.1 mole KOH), 50 ml of dimethyl sulfoxide and 6 ml of benzene. The reaction mixture was kept under an atmosphere of nitrogen and the water was azeotroped oft over a 3 to 4 hours period (130—135° C). At the end of this time the reaction mixture consisted of the potassium salt of the biphenol and was essentially anhydrous. After cooling the mixture there was added 14.35 g (0.05 moles) of 4.4 -dichlorodiphenyl sulfone and 40 ml of anhydrous dimethylsulfoxide. The reaction mixture was maintained, under a nitrogen atmosphere, between 130 and 140° C with stirring for 4 to 5 hours. The viscous orange solution was then poured into 300 ml of water in a Waring Blendor and the polymer separated by filtration and dried at 110° for 16 hours. A yield of 22.2 g (100%) of polymer with a reduced viscosity in chloroform (0.2 g per 100 ml at 25°) of 0.59 was obtained. 

The only data available to date on these polymers is the patent (50) and commercial literature. A large number of different polymers have been prepared (Table 1). The physical properties of the polymer from 4.4 -isopropylidenediphenol and 4.4 -dichlorodiphenyl sulfone are summarized in Table 10. 

The preparation of the related high molecular weight poly-1.4-phenylene sulfide has been accomplished by heating />-bromothio-phenolate salts in pyridine at 250° C (57). The commercially available polyethersulfones are reported to be prepared by condensation of 4.4 -dichlorodiphenyl sulfone with salts of biphenols in solvents such as dimethylsulfoxide at 150° C. The work of Bacon and Hill would suggest that both of these reactions might be carried out at considerably lower temperatures with copper (I) salts as catalysts. In addition, it has been demonstrated that copper (I) acetylides react quantitatively with aromatic iodides to yield tolanes (15, 77) therefore this reaction should also be the basis for a similar polymer forming reaction. 

Radel A 400 polyarylsulfone resin is made from a proprietary blend of bisphenols (believed to include hydroquinone) and dichlorodiphenyl sulfone. Victrex resin is made by other displacement reactions. 

The preliminary electron beam experiments on all aromatic polyfarylene ether sulfone)s were performed by Hedrick et al. [58] and the detailed investigation on radiation effects of these polymers were recently carried out by Lewis et al. [59]. They found that an aromatic polysulfone based on 4,4 -biphenol and 4,4 -dichlorodiphenyl sulfone exhibited the highest radiation tolerant in a systematic series of polyfarylene ether sulfone)s with "/-irradiation up to 4 x 106 Gy. 

The polysulfones are made by condensation polymerization of the potassium salt of bisphenol-A with dichlorodiphenyl sulfone, as discussed by S. R. Schulze and A. L. Baron. The polysulfonates are made from bisphenol-A and disulfonyl chlorides. They are more brittle than poly-sulfone and have been suggested by R. J. Schlott and co-workers to be used in coplymers with linear polyesters to improve the hydrolytic stability of the latter. 

Synthesis. Five different polyaryl ethers were made from the condensation product, resulting from the reaction of phenol and levulinic acid, commonly referred to as diphenolic acid, and one or more of the following monomers bisphenol A, dichlorodiphenyl sulfone, 2,6-dichloro-benzonitrile, and 4,4 -difluorobenzophenone. The resulting polymers were subsequently methylated such that the common monomer becomes (1) ... 

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