Synthesis and Property of Poly(arylene sulfone)s Containing 9,9-Diarylfluorene Moiety in the Main Chain

Abstract

ABSTRACT:Poly(arylene sulfone)s (PASs) were synthesized in quantitative yields by the oxidations of the corresponding fluorene-containing poly(arylene thioether)s, derived from 9,9-diarylfluorene-based dithiols and dihaloarenes, with 30% hydrogen peroxide in formic acid. PASs had good solubility in common organic solvents such as chloroform, N-methylpyrrolidone (NMP), and N,N-dimethylformamide (DMF). Highly transparent films were obtained by casting the chloroform solutions of PASs. PASs exhibited high glass transition and high decomposition temperatures (T g 248-355C, T d5 > 400 C under nitrogen). [doi:10.1295/polymj.PJ2006211] KEY WORDS Poly(arylene thioether) / Poly(arylene sulfone) / 9,9-Diarylfluorene / Thermal Stability / Solubility / Increasing interest has been devoted to the syntheses of high performance polymers with special property including poly(arylene sulfone)s as amorphous engineering thermoplastics. Poly(arylene sulfone)s possess excellent properties such as mechanical strength, hydrolytic stability, low flammability, and oxidative stability, making them wildely useful in various applications.1 For example, they could be the basic materials for porous and dense polymeric membranes required for gas separation or fuel cell application.2 Some polysulfones are commercially available as high performance engineering plastics such as UDEL Ò , VICTREX Ò , RADEL Ò , and so on. Aromatic polysulfones are often synthesized by direct polymerization via aromatic nucleoplilic substitution of the corresponding bis(fluoroaryl)sulfones and bisphenols as monomers.3 Ueda et al. 4 have reported the synthesis of aromatic poly(ether sulfone)s from nickel complex-mediated aromatic coupling polymerization of aromatic dichloride. An alternative way of making poly(arylene sulfone)s involves oxidation of poly(arylene thioether)s with hydrogen peroxide in formic acid. 5,6 By the replacement of thioether function with sulfone function in polymer main chain, it is expected that sulfone polymer shows, e.g., glass transition temperature (T g ) higher than the corresponding thioether polymer. Meanwhile, polymers containing 9,9-diarylfluorene moieties in the main chain have collected much interest because of their excellent properties such as high solubility and good optical properties based on the cardo structure of the 9,9-diarylfluorene moiety.7 Since polysulfones are usually hard to be soluble in ordinary organic solvents, the introduction of the fluorene skeleton seems to improve the solubility of polysulfones in addition to endowment of good optical property. We have recently prepared 9,9-diarylfluorene-based poly(arylene thioether)s with excellent physical and optical properties.8 As far as we know, no data has been reported by using of poly(arylene thioether)s containing 9,9-diarylfluorene to obtained poly(arylene sulfone)s. Therefore, we have undertaken the synthesis of poly-(arylene sulfone)s by the oxidation of the poly(arylene thioether)s, judging from the ease of procedure. This report describes the synthesis and cha...

9,9-Diarylfluorene-Based Poly(alkyl aryl ether)s: Synthesis and Property

“…These characteristic optical properties of the F-PEs come mainly from the cardo structure of the 9,9-diarylfluorene skeleton as well as the alkyl chains in the main chain. [1][2][3][4][5][6][7][8][9] In addition, the carbon filler (C 60 ) dispersing power of the F-PEs was confirmed and decreased with increase in length of the alkyl chain. Thus, the F-PEs can unambiguously be regarded as one of the potential polymer materials being used in a variety of fields including optical materials field.…”

“…The PET film had clear birefringence, as showed in Figure 8, while the films of 3a and 3d hardly showed the birefringence, in accordance with the reports on other polymers containing 9,9-diarylfluorenes. [1][2][3][4][5][6][7][8][9] Degree of retardation at 590 nm in 3d (thickness: 250 mm) was less than 3.28 nm in undrawn state, 53 and the birefringence value was remarkably low (less than 1:3 Â 10 À5 ). In the drawn film of 3d (drawn ratio is 2.0), the birefringence value was À8:9 Â 10 À4 , and the stress optical coefficient was very low (À0:15 GPa À1 ).…”

“…Such low birefringence should be attributed to the optical anisotropy decreasing effect of the cardo structure of the 9,9-diarylfluorene moiety placed in the main chain as mentioned. [1][2][3][4][5][6][7][8][9] The fluorene moiety and the two phenyl groups at the C9-position occupy different planes and are crossed at the precise angle that renders the structure most stable. Placing the aromatic rings on the different planes might disturb their one-directional folding, and thereby the optical anisotropy of the F-PEs disappears.…”

“…[1][2][3][4][5][6][7][8][9] Such optical property is caused by the presence of many aromatic rings in the 9,9-diarylfluorene moiety which occupy the different planes to disturb the interchromophore packing, effectively decreasing the optical anisotropy. Meanwhile, such polymers also display excellent filler-dispersing ability [10][11][12] in addition to their high thermal stability, [13][14][15][16] high solubility, [17][18][19] and so on.…”

Transparency and high heat resistance of cardo based poly(arylene ether)s for flexible plastic substrates

“…It also has been reported that the incorporation of trifluoromethyl, sulfonyl, ketone, and/or ether moieties between benzene rings activates aromatic halide monomers and consequently accelerates a nucleophilic displacement reaction by generating aromatic diphenolate ions from the aromatic diols and results in a high molecular weight polymer during the polycondensation. [13][14][15] This article reports new PAEs produced from a nucleophilic substitution reaction of 4-fluoro-4'(((fluorobenzoyl)phenyl)-oxy)diphenyl sulfone) (FBPODS), an ordered sequence monomer, with cardo typed aromatic diols such as 9,9-bis (4-hydroxyphenyl)fluorene (BHPF), 1,3-bis(4-hydroxyphenyl)adamantane (BHPA), and 1,1-bis(4-hydroxyphenyl)cylclohexane (BHPC). Their thermal and mechanical properties, transparency, solubility, and water uptake will also be described.…”