Poly Ketone s

A powerful and efficient method for the preparation of poly(ketone)s is the direct polycondensation of dicarboxylic acids with aromatic compounds or of aromatic carboxylic acids using phosphorus pentoxide/methanesulfonic acid (PPMA)16 or polyphosphoric acid (PPA)17 as the condensing agent and solvent. By applying both of these reagents to the synthesis of hexafluoroisopropylidene-unit-containing aromatic poly(ketone)s, various types of poly(ketone)s such as poly(ether ketone) (11), poly(ketone) (12), poly(sulfide ketone) (13), and poly- 

The molecular weights of poly(ketone)s obtained from diphenyl ketone and diphenyl sulfone are lower than those from diphenyl ether and diphenyl sulfide. The former monomers possess highly electron-withdrawing carbonyl or sulfone groups, which lower the electron density of the rings. 

Irrespective of the feed ratio of 15 and 16, the reaction proceeds homogeneously, and quantitative yields are attained with reduced viscosities between 0.13 and 0.37 dl/g. 

Four poly(ether ketone)s obtained from 2,2-bis[4-(4-fluorobenzoyl)-phenyl]-1,1,1,3,3,3-hexafluoropropane (9) or 2,2-bis[4-(4-fluorobenzoyl)-phenyl]propane (10) with Bisphenol AF (1) or Bisphenol A (4) are all soluble in chloroform, benzene, THF, and aprotic polar solvents such as DMF, DMAc, and NMP.15 Poly(ether ketone) from 9 and 1, which has the highest fluorine content, dissolves easily in ethyl acetate. 

Poly(ketone)s obtained from 2,2-bis(4-carboxyphenyl)-l 1,1,3,3,3-hexa-fluoro-propane 15 with diphenyl compounds dissolve readily in aprotic polar 

Hexafluoroisopropylidene-unit-contaming copoly(ether ketone)s and copoly-(sulfide ketone)s are also synthesized by reacting mixtures of 2,2-bis(4-carboxy-phenyl)- , 1,1,3,3,3-hexafluoropropane (15) and 2,2-bis(4-carboxyphenyl)-propane (16) with diphenyl ether or diphenyl sulfide in PPMA, respectively 

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Generally, trialkylboranes are useful intermediates in the field of organic synthesis with versatile reactivity. The polymers prepared by polyaddition between diene monomers and thexylborane are polymer homologues of trialkylboranes, which can be converted to poly(alcohol)s, poly(ketone)s, and other polymers having some functional groups (scheme 4).8-12... 

To synthesize the poly(ketone)s selectively, the reaction between the organoboron polymers and KCN was reported (scheme 6).8 After oxidation of the reaction mixture, followed by coagulation, the desired poly(ketone)s were obtained. The yielded polymers... 

Table 9.8. Thermal Properties of Poly(Ketone)s Having Hexafluoroisopropylidene Units18... 

Crystallinity of these hexafluoroisopropylidene-unit-containing poly(ketone)s is low except for poly(sulfide ketone) (13). The water contact angle for the fluorine-containing poly(ketone) films is high, being 98° for poly(ether ketone) (11), from 2,2-bis(4-carboxyphenyl)-l,l, l,3,3,3-hexafluoropropane(15) and 96° for poly(sulfide ketone) (13) from 15, whereas it is 78° for poly(ether ketone) from 2,2-bis(4-carboxy-phenyl)propane (16) and 74° for the poly(sulfide ketone) from 16. This result indicates that the substitution of isopropylidene units of poly-(ketone)s with hexafluoroisopropylidene units has a remarkable effect on the surface properties of poly(ketone) films. 

Various copolymers and terpolymers poly(ketone)s containing functional groups (phenolic or phenyl ether substrates) were prepared using ]Pd(dppp)(CH3CN)2] (BF4)2 as the catalyst precursor [124, 125]. Using the same catalytic system meso-genic 1-alkenes were also copolymerized [126]. 

High-molecular-weight poly(ketone)s and poly(ketone sulfone)s can be prepared by reacting dicarboxylic acids with aromatic compounds in the presence of trifluoromethanesulfonic acid and phosphorus pentoxide for water binding. 

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