Arylene monomer synthesis

Arylene Monomer Synthesis. Bis(triethoxysilyl)arylene monomers 1-4 were synthesized from the aryl dibromides and tetraethoxysilane (TEOS) or chlorotriethoxysilane using Barbier-Grignard or organolithium chemistry (Scheme 3). An example of the preparation of 1 from 1,4-dibromobenzene and tetraethoxysilane is as follows ... 

Similar to the synthesis of polysulfones, poly(arylene ether ketone)s can also be prepared by using either AA and BB monomers or an AB monomer. 

Robeson and Matzner were the first to report the synthesis of the sulfonation of DCDPS.205 This work makes it possible to synthesize sulfonated poly(arylene ether sulfone) with well-controlled structures. Ueda et al. used this monomer (Scheme 6.27) as a comonomer of DCDPS to react with bisphenol A and high-molecular-weight bisphenol-A-based copolymers with up to 30 mol % sulfonation achieved.206 Biphenol-based copolymers with up to 100 mol % sulfonation were recently reported by Wang et al.207... 

In 1996, Wegner et al. published the synthesis of poly(oligophenylenevinyle-ne)s (96), consisting of biphenylene-, terphenylene- and quinquephenylene moieties as aromatic building blocks, via Suzuki-type aryl-aryl cross coupling of AA/BB-type monomers [121]. By judicious choice of the arylene moieties, the optical properties of the resulting polymers can be tailored within a wide range. 

Postsulfonation of polymers to form PEMs can lead to undesirable side reactions and may be hard to control on a repeatable basis. Synthesis of sulfonated macromolecules for use in PEMs by the direct reaction of sulfonated comonomers has gained attention as a rigorous method of controlling the chemical structure, acid content, and even molecular weight of these materials. While more challenging synthetically than postsulfonation, the control of the chemical nature of the polymer afforded by direct copolymerization of sulfonated monomers and the repeatability of the reactions allows researchers to gain a more systematic understanding of these materials properties. Sulfonated poly(arylene ether)s, sulfonated poly-(imide)s, and sulfonated poly(styrene) derivatives have been the most prevalent of the directly copolymerized materials. 

The synthesis of other poly(arylene ether)s containing thiophene units concerned the reaction of two activated halides containing thiophene (structures 8 and 9) with bisphenol A [44,45]. The polymers from the monomers of structures 8 and 9 and bisphenol A had intrinsic viscosities (NMP, 25 °C) of 1.23 and 0.43 dL/g and Tgs of 158 and 120°C, respectively. 

Oxidative polymerization of aryl disulfides has been carried out under high dilution conditions for the preparation of cyclic arylene sulfides for synthesizing cyclic arylene sulfide polymers. The readily available diphenyl disulfide and dichloro disulfide with diphenyl sulfide, diphenyl ether, or p-xylene are useful monomers for the synthesis of the corresponding cyclic oligo(thio arylene)s. The reaction scheme is shown in Fig. 30 [101]. 

The application of Heck coupling polycondensation is not limited to the synthesis of poly(arylene vinylene)s via the alkenylation of haloarenes in simple monomer systems but includes a variety of self- and cross-coupling reactions involving reactants with various functionalities. For instance, the polycondensation of diiodoarene with bis(acrylamido)arene by the Pd(OOCCH3)2—P (o-C6H4—CH3)3 catalyst yields respective aromatic polycinnamamide [106] ... 

Bis(3-aminophenyl)arylene ethers are useful monomers to prepare polyimides of lower Tg s. For example, l,3-bis(3-aminophenoxy)benzene has been used as building blocks for various thermally processable PI systems. The compound was originaly synthesized by Fink [6] according to the following Ullmann synthesis under rather harsh conditions. 

Synthesis of polydiacetylenes from novel monomers having two diacetylene units linked by an arylene group were characterized by solid-state NMR. ... 

Harrison WL, Hickner MA, Kim YS, MaGrath JE (2005) Poly(arylene ether sulphone) copolymers and related systems from disulphonated monomer building blocks synthesis, characterization and performance—a topical review. Fuel Cells 5 201-212... 

Novel organometallic poly(arylene)s with 1,3-type (cyclobutadiene)cobalt moieties 27 in the main chain are prepared by Ni(0)-mediated dehalogenative polycondensation of monomers having (cyclobutadiene)cobalt moieties [51], The polymers with of 20 kDa exhibit thermotropic liquid crystallinity. The synthesis of a variety of homometallic and heterometallic oligomers and polymers such as 28 is possible via nucleophilic aromatic substitution reactions of dichlorophenylene-Fe Cp and dihydroxyphenylene-Ru Cp complexes in DMF in the presence of K2CO3 [52]. 

Scheme 2.17 Synthesis of hb poly(arylene ether)s from monomers containing nitro group (a) via selective and sequential S vjAr (preferential fluorine displacement followed by nitro displacement) reaction of As-and BC-type monomers (b) via nitro displacement reaction of A2C-type monomer. Taken from Ref. [76],...

I.S. Chung, S.Y. Kim, Poly(arylene ether)s via nitro displacement reaction synthesis of poly(biphenylene oxide)s containing trifluoromethyl groups from AB type monomers. Macromolecules 33 (26)(2000) 9474-9476. 

YJ. Kim, M.A. Kakimoto, S.Y Kim, Synthesis of hyperbranched poly(arylene ether) from monomer contaiiung nitro group kinetically controlled growth of polymer chain through dynamic exchange of end functional groups. Macromolecules 39 (21)... 

S. Banerjee, Synthesis and characterization of novel hyperbranched poly(arylene ether) from a AB2 monomer, J. Polym. Mater. 24 (3)... 

S. Banerjee, H. Komber, L. HauBler, B. Voit, Synthesis and characterization of hyperbranched poly(arylene ether)s from a new activated trifluoro B3 monomer adopting an A2 + B3 approach, Macromol. Chem. Phys. 210(16) (2009) 1272-1282. 

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