Bisphenols, poly condensation with

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. 

Difluorothianthrene, i.e., 2,7-difluoro-9,10-dithiaanthracene, c.f. Figure 5.8, is a monomer for poly(aryl ether thianthrene)s. This monomer is a high melting crystalline solid that sublimes under reduced pressure, simplifying the purification for polymer S5mthesis. It can be condensed with a bisphenol to yield poly(aryl ether thianthrene)s. ... 

The data for high-temperature polycondensation of different disodium salts of the bisphenols with 4,4 -dichlorodiphenylsulfone (DCDPS) are used [47], The bisphenols denomination, their conventional signs and also the values of poly condensation rate constants k and En are adduced in Table 2. Besides, the kinetic curves conversion degree — reaction duration (Q -1) of polycondensation, adduced in the work [47], were used. 

Mikitaev, A. K. Korshak, V. V Musaev, Yu. I. Storozhuk, I. P. Correlation analysis of poly condensation reaction of disodium salts of bisphenols with 4,4 -dichlo-rodiphenylsulfone. In collection Problems of Physics-chemistry of Polymers. Ed. Mikitaev, A. Zelenev, Yu. Nal chik, KBSU, 1972,29-38. 

Pilati, F., Fiorini, M., and Berti, C., Effects of Catalysts in the Reactive Blending of Bisphenol A Polycarbonate with Poly(aIkylene Terephthalate)s, in Transreactions in Condensation Polymers, S. Fakirov, ed., WUey-VCH, Weinheim, 1999. 

Benzoin methyl ethers have been incorporated into a polycarbonate chain. The synthesis was achieved by polycondensing bisphenol A with phosgene in the presence of 4,4 -dihydrobenzoin methylether [216]. Irradiation of the resulting poly condensate in the presence of methyl methacrylate... 

Fig. 7.7 MALDI-TOF mass spectrum of a fraction of polycarbonate prepared by triethylamine-catalyzed hydrolytic poly condensation of bisphenol-A bischloroformiate (Cl000 means cycle with DP = 100). Reproduced from Ref. [44, Fig. 6] with permission (Copyright Wiley-VCH Verlag GmbH Co KGaA)...

Montaudo and co-workers have used direct pyrolysis mass spectrometry (DPMS) to analyse the high-temperature (>500°C) pyrolysis compounds evolved from several condensation polymers, including poly(bisphenol-A-carbonate) [69], poly(ether sulfone) (PES) and poly(phenylene oxide) (PPO) [72] and poly(phenylene sulfide) (PPS) [73]. Additionally, in order to obtain data on the involatile charred residue formed during the isothermal pyrolysis process, the pyrolysis residue was subjected to aminolysis, and then the aminolyzed residue analysed using fast atom bombardment (FAB) MS. During the DPMS measurements, EI-MS scans were made every 3 s continuously over the mass range 10-1,000 Da with an interscan time of 3 s. 

Hexafluoroisopropylidene-unit-containing aromatic poly(ether ketone)s were first synthesized from an alkaline metal salt of Bisphenol AF (1) and 4,4 -difluoro-benzophenone.14 Cassidy and co-workers prepared hexafluoroisopropylidene-unit-containing poly(ether ketone)s by condensing 2,2-bis[4-(4-fluorobenzoyl)-phenyl]-l,l,l,3,3,3-hexafluoropropane (9) and 2,2-bis[4-(4-fluorobenzoyl)-phenyljpropane (10) with Bisphenol AF (1) or Bisphenol A (4) (Scheme 7).15 The reactions are nucleophilic aromatic displacements and were conducted in DMAc at 155- 160°C with an excess of anhydrous potassium carbonate. After 3 to 6 h of reaction, high-molecular-weight poly(ketone)s are obtained in high yields. 

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. 

The telechelica,(i -bis(2,6-dimethylphenol)-poly(2,6-dimethylphenyl-ene oxide) (PP0-20H) [174-182] is of interest as a precursor in the synthesis of block copolymers [175] and thermally reactive oligomers [179]. The synthesis has been accomplished by five methods. The first synthetic method was the reaction of a low molecular weight PPO with one phenol chain end with 3,3, 5,5 -tetramethyl-l,4-diphenoquinone. This reaction occurred by a radical mechanism [174]. The second method was the electrophilic condensation of the phenyl chain ends of two PPO-OH molecules with formaldehyde [177,178], The third method consists of the oxidative copolymerization of 2,6-dimethylphenol with 2,2 -di(4-hydroxy-3,5-di-methylphenyl)propane [176-178]. This reaction proceeds by a radical mechanism. A fourth method was the phase transfer-catalyzed polymerization of 4-bromo-2,6-dimethylphenol in the presence of 2,2-di(4-hy-droxy-3,5-dimethylphenyl)propane [181]. This reaction proceeded by a radical-anion mechanism. The fifth method developed was the oxidative coupling polymerization of 2,6-dimethylphenol (DMP) in the presence of tetramethyl bisphenol-A (TMBPA) [Eq. (57)] [182],... 

New cyclolinear phosphazene poly(ether ketones) (224a, b) have been synthesized by the condensation of the new spiro-substituted cyclophosphazene (223) with 4,4 -difluorobenzophenone and a bisphenol. ... 

It should be expected that the influence of the chain segment mobility is most pronounced when the photochrome groups are inserted into a semirigid polymer backbone instead of being attached as mobile side groups in copolymers. Therefore, polyesters have been prepared by condensation of bis-hydroxymethyl-spirobenzopyrans with bisacid dichlorides.followed by polyesterification with bisphenol-A43,46). Thus, a photo-chromic poly(bisphenol-A-pimelate) (polyester XI) of the following formula was obtained. 

The synthesis of poly(ether imide)s by condensation of the disodium salt of bisphenol-A with bis(chlorophthalimide)s under microwave irradiation conditions has been described by Zhang et al. (Scheme 14.21) [50]. The polymerization reactions were performed under phase-transfer catalysis (PTC) conditions in o-dichlorobenzene solution. For this purpose a mixture of 16.12 mmol bis(chloro-phthalimide)s and 16.12 mmol disodium salt of bisphenol-A in 60 mL o-dichlorobenzene with 0.56 mmol hexaethylguanidinium bromide was irradiated in a domestic microwave oven for 25 min and the product was precipitated by addition of methanol. The polymerization reactions, in comparison with those under the action of conventional heating, proceeded rapidly (25 min compared with 4 h at 200 °C) and polymers with inherent viscosities in the range 0.55 to 0.90 dL g were obtained. 

A fluorinated poly(arylene ether sulfide) (PSI) is prepared from the condensation of bis-(pentafluorophenyl)-sulfide with 4,4 -(trifluoromethylphenyl-isopropyhdene)diphenol, which is a methyl fluorinated bisphenol A. " ... 

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 technique of phase-transfer catalysis has been extensively apphed to the two-phase polycondensation using various phase-transfer catalysts, such as quaternary ammonium and phosphonium salts, crown ethers and poly(ethylene glycol)s. 5 - 53,75,87,n9,i5i Various types of condensation polymers such as aromatic polysulfonates and polysulfides, aromatic polyethers, ahphatic and aromatic polysulfides, and carbon-carbon chain polymers of high molecular weights hy the phase-transfer catalyzed polycondensation fi-om combinations of aromatic disulfonyl chlorides, phosphonic dichlorides, activated aromatic dichlorides, and aliphatic dihahdes, with bisphenol, aliphatic and aromatic dithiols, and active ethylene compounds. The two-phase polycondensation was generally carried out in a water-immiscible organic solvent-aqueous alkaline solution system at room temperature. The method of polycondensation offers a highly versatile and convenient synthetic method for a variety of condensation polymers. 

Various synthetic approaches have been demonstrated for the synthesis of PAEs since early days [35 0], PAEs were synthesized by Ullmann condensation between bisphenols and aryl fcis-halide monomers using Cu(I) salt/pyridine as catalyst [36], General Electric developed the first commercially successful PAE poly(2,6-dimethyl phenylene oxide) (PPO) [38], It was prepared by oxidative coupling of 2,6-dimethyI phenol. However, this process has its own restrictions, because it does not allow much structural variation or inclusion of any electron-withdrawing group into the polymer main chain. First attempts to synthesize polysulfones (PSF) were successfully done by Friedel-Crafts sulfonylation reaction of arylenedisulfonyl chlorides, for example, diphenyl ether-4,4 -disulfonyl chloride with diaryl ethers, for example, diphenyl ether, or by self-condensation of 4-phenoxy benzene sulfonyl chloride in the presence of FeCls [41], Whereas the former reaction involves side reactions (sulfonylation not only in the para- but also in the ort/io-position), the latter produces only the desired linear all-para products. 

The poly(ether ketone)s 9 were prepared by condensation of monomer 6 with various bisphenols under the usual reaction conditions (6). Polyimides 10 (R = methyl) and 11 (R = cyclohexyl) were synthesized via the poly(amic acid) and thermal imidiza-tion of the films by condensation of monomers 7 and 8 with various dianhydrides (7 8). The structures of the polymers are shown in Scheme 4. 

Polyetherether Ketones, Polysulfones, and Acetal Resins. The poly(etherether ketones), or PEEK, can be prepared by condensation of the dipotassium salt of hydroquinone or bisphenol A with 4,4 -difluorodiphenyl ketone at temperatures in excess of 300 C. 

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