Synthesis and curing behavior of alkyl-substituted poly(aryl ether ketone)s having a crosslinkable styryl group at chain ends

Abstract

Crosslinkable alkyl‐substituted poly(aryl ether ketone)s (PEKs) bearing a styryl group at both chain ends were synthesized by nucleophilic substitution reaction of 1,1′‐(p‐phenyl‐enedioxy)bis[2‐methyl‐4‐(4‐fluorobenzoyl)benzene] with an excess aromatic diol in the presence of a base, followed by the reaction of the terminal phenol group with chloromethylstyrene. The aromatic diols used in this study were hydroquinone and resorcinol. The molecular weight of the polymer determined by GPC and 1H NMR agreed with each other and close to the theoretical value calculated from the feed ratio. The polymer was soluble in N,N‐dimethylacetamide and tetrahydrofuran, but insoluble in acetone and methanol. From DSC analysis, the polymer was thermally crosslinked around 220°C. The addition of dicumyl peroxide as a radical generator in the polymer decreased the curing temperature. The cured polymer showed high thermal stability up to 420°C under nitrogen. © 1997 John Wiley & Sons, Inc.

Phthalonitrile-functional multiple arylene ether nitrile-containing phthalazinone moiety: facile synthesis, curing, and properties

“…In summary, our results demonstrate that certain reaction of phthalonitrile rather than pendant cyano groups occurred resulting in phthalazinone networks containing s -triazine units. 10,11 Further efforts in detailed mechanism are currently under way by our group.…”

“…Cross-linking has been well known for its impact on the performance of polymer systems. 10 Essentially, the cyano group of PAENs appears to be a potential site for polymer cross-linking through trimerization strategy. 11 Unfortunately, the cyclization of pendent cyano units is rather difficult, since extremely harsh conditions are usually required for this termolecular reaction.…”

Phthalonitrile-functional multiple arylene ether nitrile-containing phthalazinone moiety: facile synthesis, curing, and properties

“…In summary, our results demonstrate that certain reaction of phthalonitrile rather than pendant cyano groups occurred resulting in phthalazinone networks containing s -triazine units. 10,11 Further efforts in detailed mechanism are currently under way by our group.…”

“…Cross-linking has been well known for its impact on the performance of polymer systems. 10 Essentially, the cyano group of PAENs appears to be a potential site for polymer cross-linking through trimerization strategy. 11 Unfortunately, the cyclization of pendent cyano units is rather difficult, since extremely harsh conditions are usually required for this termolecular reaction.…”

Amorphous Poly-2,7-fluorene Networks

“…We chose the thermal conditions based on the onset of the 4-phenylethenyl end group cross-linking exotherm as observed by modulated DSC. Detailed studies of the thermal cross-linking chemistry of similar 4-phenylethenyl-terminated oligomers can be found elsewhere. 12a,

1 Thin film PL-spectra of 8a − d (λ exc. = λ max ).

…”

Durable crosslinked films based on poly (arylene ether nitrile) materials for ultrahigh temperature applications over 300°C

“…In an attempt to obtain a higher temperature resistance of PEN, we used a method which converted the polymer from a linear structure to a three-dimensional network structure. Generally, the alkenyl, 18,19 alkynyl, 20, 21 methyl, 22 epoxy, 23 nitrile, 24,25 and phthalonitrile 26 groups are used for crosslinking reactions of thermoplastic polymers. For traditional PEN, the nitrile group on the side of the molecular chain was a unique crosslinking reaction site.…”

Phthalonitrile-functional multiple arylene ether nitrile-containing phthalazinone moiety: facile synthesis, curing, and properties

“…In summary, our results demonstrate that certain reaction of phthalonitrile rather than pendant cyano groups occurred resulting in phthalazinone networks containing s -triazine units. 10,11 Further efforts in detailed mechanism are currently under way by our group.…”

“…Cross-linking has been well known for its impact on the performance of polymer systems. 10 Essentially, the cyano group of PAENs appears to be a potential site for polymer cross-linking through trimerization strategy. 11 Unfortunately, the cyclization of pendent cyano units is rather difficult, since extremely harsh conditions are usually required for this termolecular reaction.…”

Amorphous Poly-2,7-fluorene Networks

“…We chose the thermal conditions based on the onset of the 4-phenylethenyl end group cross-linking exotherm as observed by modulated DSC. Detailed studies of the thermal cross-linking chemistry of similar 4-phenylethenyl-terminated oligomers can be found elsewhere. 12a,

1 Thin film PL-spectra of 8a − d (λ exc. = λ max ).

…”

Durable crosslinked films based on poly (arylene ether nitrile) materials for ultrahigh temperature applications over 300°C

“…In an attempt to obtain a higher temperature resistance of PEN, we used a method which converted the polymer from a linear structure to a three-dimensional network structure. Generally, the alkenyl, 18,19 alkynyl, 20, 21 methyl, 22 epoxy, 23 nitrile, 24,25 and phthalonitrile 26 groups are used for crosslinking reactions of thermoplastic polymers. For traditional PEN, the nitrile group on the side of the molecular chain was a unique crosslinking reaction site.…”

Phthalonitrile-functional multiple arylene ether nitrile-containing phthalazinone moiety: facile synthesis, curing, and properties

“…In summary, our results demonstrate that certain reaction of phthalonitrile rather than pendant cyano groups occurred resulting in phthalazinone networks containing s -triazine units. 10,11 Further efforts in detailed mechanism are currently under way by our group.…”

“…Cross-linking has been well known for its impact on the performance of polymer systems. 10 Essentially, the cyano group of PAENs appears to be a potential site for polymer cross-linking through trimerization strategy. 11 Unfortunately, the cyclization of pendent cyano units is rather difficult, since extremely harsh conditions are usually required for this termolecular reaction.…”

Amorphous Poly-2,7-fluorene Networks

“…We chose the thermal conditions based on the onset of the 4-phenylethenyl end group cross-linking exotherm as observed by modulated DSC. Detailed studies of the thermal cross-linking chemistry of similar 4-phenylethenyl-terminated oligomers can be found elsewhere. 12a,

1 Thin film PL-spectra of 8a − d (λ exc. = λ max ).

…”

Durable crosslinked films based on poly (arylene ether nitrile) materials for ultrahigh temperature applications over 300°C

“…In an attempt to obtain a higher temperature resistance of PEN, we used a method which converted the polymer from a linear structure to a three-dimensional network structure. Generally, the alkenyl, 18,19 alkynyl, 20, 21 methyl, 22 epoxy, 23 nitrile, 24,25 and phthalonitrile 26 groups are used for crosslinking reactions of thermoplastic polymers. For traditional PEN, the nitrile group on the side of the molecular chain was a unique crosslinking reaction site.…”