Synthesis of aromatic poly(ether amide amide ether ketone ketone)s by electrophilic Friedel–Crafts solution polycondensation

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A new monomer, 2,6-bis(4-phenoxybenzoyl)naphthalene (BPOBON), was easily synthesized via simple synthetic procedures from readily available materials. A series of novel poly(aryl ether ketone)s containing both 2,6-naphthylene moieties and amide linkages in the main chains were prepared by the Friedel-Crafts acylation solution copolycondensation of isophthaloyl chloride with a mixture of BPOBON and N,N'-bis(4-phenoxybenzoyl)-1,4-phenylenediamine (BPBPPD), over a wide range of BPOBON/BPBPPD molar ratios, in the presence of anhydrous AlCl 3 and N-methylpyrrolidone in 1,2-dichloroethane. All the polymers are semicrystalline and had remarkably increased T g s over the conventional PEEK and PEKK due to the incorporation of naphthalene and amide linkages in the main chains. The polymers with 50-70 mol % BPOBON had not only high T g s of 179-186C, but also moderate T m s of 321-328 C, which are very suitable for the melt processing. These polymers had tensile strengths of 101.5-107.1 MPa, Young's moduli of 2.13-2.39 GPa, and elongations at break of 11.8-13.7% and exhibited excellent thermal stability and good resistance to organic solvents.

“…2,6‐Naphthalenedicarboxylic acid (Shanghai Chemical Reagent) were used as received. BPBPPD was prepared according to our previous procedure …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of novel poly(aryl ether ketone)s containing both 2,6‐naphthylene moieties and amide linkages in the main chains

Cai

Chen

et al. 2013

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“…To modify the aramid properties, aromatic poly(ether ketone amide)s have been synthesized by polycondensation of diaroyl chlorides bearing ether‐ketone linkages with aromatic diamines containing ether linkages or by direct polycondensation of 3‐[4‐(3‐aminophenoxybenzoyl)phenoxy]benzoic acid . In addition, the nucleophilic aromatic substitution polycondensation of bisfluoro‐monomers containing ketone and amide groups with bisphenols and the electrophilic acylation polycondensation of aromatic ethers containing amide groups with diaroyl chlorides have also been used to prepare aromatic poly(ether ketone amide)s . These polyamides displayed high thermal stability, good flexibility and solubility, as well as relatively lower T g values than aramids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of poly(ether ketone amide)s containing 4‐aryl‐2,6‐ diphenylpyridine moieties by a heterogeneous palladium‐catalyzed polycondensation of aromatic diiodides, aromatic diamines, and carbon monoxide

Tang

Huang

Zhu

et al. 2018

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New aromatic poly(ether ketone amide)s containing 4-aryl-2,6-diphenylpyridine units were prepared by the heterogeneous palladium-catalyzed carbonylative polymerization of aromatic diiodides with ether ketone units, aromatic diamines bearing pyridine groups, and carbon monoxide. Polymerizations were performed in N,N-dimethylacetamide (DMAc) at 120°C in the presence of a magnetic nanoparticles-supported bidentate phosphine palladium complex [Fe 3 O 4 @SiO 2 -2P-PdCl 2 ] as catalyst with 1,8-diazabicycle[5,4,0]-7-undecene (DBU) as base and generated poly(ether ketone amide)s with inherent viscosities up to 0.79 dL/g. All the polymers were soluble in many organic solvents. These polymers showed glass transition temperatures between 219°C and 257°C and 10% weight loss temperatures ranging from 467°Cto 508°C in nitrogen. These polyamides could be cast into transparent, flexible, and strong films from DMAc solution with tensile strengths of 86.4 to 113.7 MPa, tensile moduli of 2.34 to 3.19 GPa, and elongations at break of 5.2% to 6.9%. These polymers also exhibited good optical transparency with an ultraviolet-visible absorption cut-off wavelength in the 371 to 384-nm range. Importantly, the new heterogeneous palladium catalyst can easily be recovered from the reaction mixture by simply applying an external magnet and recycled at least 8 times without significant loss of activity. Our catalytic system not only avoids the use of an excess of PPh 3 and prevents the formation of palladium black, but also solves the basic problems of palladium catalyst recovery and reuse. KEYWORDS carbon monoxide, carbonylation, heterogeneous catalysis, palladium-catalyzed polycondensation, poly(ether ketone amide)

“…Aromatic poly (ether ketone amide)s could be prepared by polycondensation of aromatic diacids or acid chlorides bearing ether ketone units with aromatic diamines with ether linkages or by direct polycondensation of 3‐[4‐(3‐aminophenoxybenzoyl)phenoxy] benzoic acid . In addition, the nucleophilic substitution polycondensation of bisfluoro‐monomers containing ketone and amide groups with bisphenols and the electrophilic acylation polycondensation of aromatic ethers containing amide groups with diaroyl chlorides have also proven to be effective routes to aromatic poly (ether ketone amide)s . These polyamides containing ether‐ketone linkages displayed high thermal stability, good flexibility, and solubility, as well as relatively lower T g values than aramids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of new fluorinated aromatic poly (ether ketone amide)s containing cardo structures by a heterogeneous palladium‐catalyzed carbonylative polycondensation

Liu

Zou

Zhang

et al. 2018

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New fluorinated aromatic poly (ether ketone amide)s containing cardo structures were prepared by a heterogeneous palladium‐catalyzed polycondensation of fluorinated aromatic diiodides with ether ketone units, aromatic diamines containing cardo groups, and CO. Polymerizations were conducted in N,N‐dimethylacetamide at 120°C using 6 mol% of magnetic nanoparticles‐supported bidentate phosphine palladium (II) complex [Fe3O4@SiO2‐2P‐PdCl2] as catalyst and 1,8‐diazabicyclo[5,4,0]‐7‐undecene as base and resulted in fluorinated cardo poly (ether ketone amide)s with inherent viscosities up to 0.75 dL/g. All the polymers were readily soluble in many organic solvents and could afford transparent, flexible, and strong films by solution casting. These polymers showed good thermal stability with the glass transition temperature of 237°C–258°C, the temperature at 5% weight loss of 462°C–477°C in nitrogen. These polymer films also exhibited good mechanical properties, excellent electrical and dielectric performance, and high optical transparency. The incorporation of bulky fluorinated groups and cardo structures into polymer backbone has played an important role in the improvement of solubility, dielectric performance, and optical properties. Importantly, the heterogeneous palladium catalyst can easily be recovered from the reaction mixture by simply applying an external magnet and recycled up to 7 times without significant loss of catalytic activity.