No abstract

1,1-Bis(4-hydroxyphenyl)-1-(4-phenoxyphenyl)-1-phenylmethane (BHPPPPM), a new bisphenol monomer, was synthesized with 65% yield from 4-benzoyl diphenyl ether in a one-pot, two-step synthetic procedure. Four new poly(aryl ether ketone)s (PAEKs) bearing (4-phenoxyphenyl)triphenylmethane moieties were prepared from BHPPPPM with four difluorinated aromatic ketones via a nucleophilic substitution reaction. The polycondensation proceeded in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the new PAEKs in nearly quantitative yields with inherent viscosities of 0.60-0.78 dL g À1 . The resulting PAEKs having number-average molecular weights in the range of 29,500-34,200 g mol À1 with the polydispersity index ranged from 1.94 to 2.01 are all amorphous and show high glass transition temperatures ranging from 174 C to 196 C, excellent thermal stability, and the temperatures at the 5% weight loss are over 500 C with char yields above 60% at 700 C under nitrogen atmosphere. These new PAEKs are all soluble in polar aprotic solvents such as N-methyl-2-pyrrolidone and N,N 0 -dimethylacetamide and could also be dissolved in chloroform and tetrahydrofuran. All the polymers formed transparent, strong, and flexible films with tensile strengths of 78-85 MPa, tensile moduli of 1.9-2.4 GPa, and elongations at break of 7-10%.

A novel facile solid‐phase organic synthesis of aryl vinyl ethers by reaction of polystyrene‐supported 2‐phenylsulfonylethanol with phenols under Mitsunobu conditions and subsequent elimination reaction with DBU has been developed. The advantages of this method include straightforward operation, good yield and high purity of the products. Alternatively, a typical example of Suzuki coupling reaction on‐resin was further applied to prepare 4‐phenylphenyl vinyl ether for extending this method.

Several poly(arylene ether nitrile) (PAEN) copolymers containing multi-methyl and cardo xanthene groups were synthesized by nucleophilic substitution reaction of 2,6-difluorobenzonitrile with varying molar ratios of 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)xanthene (BDMHPX) and hydroquinone (HQ) (80/20-40/60) in N-methyl-2-pyrrolidone (NMP) in the presence of anhydrous potassium carbonate. These new PAENs had inherent viscosities between 0.56 and 0.68 dL g -1 , and their weight-average molecular weights and number-average molecular weights were in the range of 33,300-36,500 g mol À1 and 17,300-18,400 g mol À1 , respectively. All polymers were amorphous and soluble in dipolar aprotic solvents such as NMP and N,N-dimethylacetamide and even in THF and chloroform at room temperature. These PAENs showed glass transition temperatures (T g s) between 248 C and 289 C, and the T g values were found to increase with increase of the BDMHPX content in the polymeric main. Thermogravimetric analysis showed that all PAENs were stable up to 400 C, with 5% weight loss temperatures ranging from 427 C to 448 C and char yields of 57-61% at 700 C under nitrogen atmosphere. All new PAENs could be cast into strong and flexible films with a tensile strength of 93-115 MPa, elongation at break of 10-12%, and tensile modulus of 3.3-3.5 GPa.

A novel monomer of tetrachloroterephthaloyl chloride (TCTPC) was prepared by the chlorination of terephthaloyl chloride catalyzed by ferric chloride at 175-1808C for 10 h and confirmed by FTIR, MS, and elemental analysis. Five new polychloro substituted poly (aryl ether ketone sulfone)s (PEKSs) with inherent viscosities of 0.68-0.75 dL/g have been prepared from 4,4 0 -diphenoxydiphenylsulfone, 4,4 0 -bis(2-methylphenoxy) diphenylsulfone, 4,4 0 -bis(3-methylph-enoxy)diphenylsulfone, 4,4 0 -bis(2,6-dimethylphenoxy)diphenylsulfone, and 4,4 0 -bis(1-naphthoxy)-diphenylsulfone with TCTPC by electrophilic Friedel-Crafts acylation in the presence of DMF with anhydrous AlCl 3 as a catalyst in 1,2-dichloroethane, respectively. These polymers having weight-average molecular weight in the range of 76,600-83,900 are all amorphous and show high glass transition temperatures ranging from 213 to 2508C, the 5% weight loss temperature over 4508C, high char yields of 60-67% at 7008C in nitrogen and good solubility in CHCl 3 and polar solvents such as DMF, DMSO, and NMP at room temperature. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 85.1-90.8 MPa, Young's moduli of 2.52-3.24 GPa, and elongations at break of 21.2-27.2%.