Synthesis and characterization of fluorinated polyetherketones prepared from decafluorobenzophenone

Mercer, Frank W.; Fone, Matilda; Reddy, V. N.; Goodwin, Andy A

doi:10.1016/s0032-3861(96)00700-8

Cited by 33 publications

(22 citation statements)

References 16 publications

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“…Using the same theoretical chemical shift predictive approach as before, [26] these new peaks have been assigned to the aromatic fluorine atoms (a 0 ) and (b 0 ) of tetrafluorophenyl-degraded species as indicated in the same figure. The final product related to Spectrum D has also been investigated by 1 H NMR, and the resulting spectrum has confirmed the results from 19 F NMR. In 1 H NMR spectrum (not shown), the original polymer shows two doublet signals with J H-H coupling constant of 8 Hz at 7.38 and 7.01 ppm in the aromatic region, which are attributed to the ortho-and meta-hydrogen atoms of 6F-BPA units.…”

Section: Highly Fluorinated Poly(arylene Ether Ketone) Prepared By a supporting

confidence: 61%

“…Notable deviations of M n from the calculated value only appear when r becomes larger than 0.96. Obviously this deviation was caused by the side reaction at ortho-positions, which consumed extra phenol group of 6F-BPA and caused a change in r. Equation (1) indicates that close to r ¼ 1a small variation in r causes a large change in the molecular weight. The fact that the molecular weight deviation is observed only when r is very close to 1 indicates that the extent of the side reaction at the ortho-positions is minor under this reaction condition.…”

Section: Cah 2 -Mediated Reactionmentioning

confidence: 99%

“…Fluorinated poly(arylene ether ketone)s (FPAEK) [1][2][3][4][5] are conventionally prepared by the polycondensation of the phenol groups of hexafluorobisphenol A (6F-BPA) with para-fluorines of bis(pentafluorophenyl) ketone (BPK) using a nucleophilic aromatic substitution reaction (S N Ar), [6][7][8][9][10] which has been traditionally used for the preparation of nonfluorinated poly(arylene ether)s. [11,12] The major problem of this reaction when applied to the preparation of FPAEK is the high tendency of a side reaction at the ortho-fluorines of BPK, [3,4] which are activated by the strong electronwithdrawing effect of the ketone group. [10] This side reaction leads to the formation of branched and eventually crosslinked structures.…”

Section: Introductionmentioning

confidence: 99%

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Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction

Ding

Day

Robertson

et al. 2004

Macro Chemistry & Physics

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Summary: A new reaction procedure has been developed for the polycondensation of hexafluorobisphenol A (6F‐BPA) with bis(pentafluorophenyl) ketone (BPK) in dimethylacetamide (DMAc). In this reaction, CaH2 has been used as a base to facilitate the formation of the phenolate; an alkali metal fluoride was used as a catalyst. Unlike the conventional polycondensation reactions, this procedure avoided producing water during the reaction, and hence, azeotropic distillation with the assistant of a low‐polar co‐solvent is not required. This improvement maintains the high polarity of the reaction medium; consequently, the selectivity of the reaction at the para‐position of BPK is significantly enhanced and polymers with high molecular weights ($\overline M _{\rm n}$ ca. 30 000 Da) can be obtained with very low branching contents (less than 3 mol‐%) and free of any cross‐linked gel particles. In addition to avoiding the formation of water in the reaction, the use of CaH2 also reduced the concentration of the fluoride ion in the solution. These effects minimize chain degradation reactions such as hydrolysis. The use of CaO instead of CaH2 for this reaction produces similar effects. In the case of CaO, traces of water can be introduced into the reaction. The presence of trace amounts of water increases the polycondensation rate, probably due to the enhanced ionization of the phenolate. However, it also causes a hydrolysis of polymer chains, resulting in the elimination of the ketone group in the polymer backbone. Fortunately, this side reaction is highly water and temperature dependent, and can be efficiently prevented by using CaH2 or conducting the reaction at a lower temperature (<65 °C).CaH2‐mediated polycondensation for the preparation of highly fluorinated poly(arylene ether ketone).imageCaH2‐mediated polycondensation for the preparation of highly fluorinated poly(arylene ether ketone).

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Section: Highly Fluorinated Poly(arylene Ether Ketone) Prepared By a supporting

confidence: 61%

Section: Cah 2 -Mediated Reactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction

Ding

Day

Robertson

et al. 2004

Macro Chemistry & Physics

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“…[1][2][3] Recently, poly(aryl ether ketone)s (PEKs) containing 2,3,5,6-tetrafluoro-1,4-phenylene moieties were synthesized from perfluorobenzophenone. 4 2,3,4,5,6-Pentafluorobenzoic acid (PFBA) is a valuable intermediate for pharmaceuticals, pesticides, perfumes, cosmetics and so on, and it is available as a commercial product. PFBA is a very useful raw material for making fluorine-containing PEKs.…”

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confidence: 99%

Synthesis of Thermally Cross-Linkable Fluorine-containing Poly(aryl ether ketone)s I. Phenylethynyl Terminated Poly(aryl ether ketone)s

Kimura

Nishichi

Yamashita

2002

Polym J

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ABSTRACT:Fluorine-containing poly(aryl ether ketone)s (PEKs) derived from 2,3,4,5,6-pentafluorobenzoic acid (PFBA) exhibit outstanding solubility, thermal stability, low dielectric constant, low moisture absorption and high transparency. Hence, they are expected to be available for optical and electric materials. In such applications, excellent solubility is of great advantage for making thin film and coating. Contrary to this advantage, this is of disadvantage from a point of solvent resistance. Thermally cross-linkable fluorine-containing PEKs terminated with phenylethynyl moiety (PEK-PEP) are synthesized to improve the solvent resistance in this study. Cross-linking reaction occurs over 320• Cand it brings about not only the outstanding solvent resistance but also the increase of T g . Relationship between the cross-linking density and T g can be fundamentally interpreted by configurational entropy theory. Furthermore, the cured PEK-PEPs possess excellent thermal stability with the 10% weight loss temperature in the range from 544 to 598• C.

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“…4 Recently, PEKs containing 2,3,5,6-tetrafluoro-l,4-phenylene moieties were synthesized from perfluorobenzophenone. 5 2,3,4,5,6-Pentafluorobenzoic acid (PFBA) is a valuable intermediate for pharmaceuticals, pesticides, perfumes, cosmetics and so on, and it is available as a commercial product. The authors had reported the synthesis and characterization of novel fluorinated PEKs containing 2,3,5,6-tetrafluoro-1,4-phenylene moieties derived from PFBA.…”

mentioning

confidence: 99%

Synthesis of Novel Fluorine-Containing Poly(aryl ether nitrile)s Derived from 2,3,4,5,6-Pentafluorobenzonitrile

Kimura

Tabuchi

Nishichi

et al. 2001

Polym J

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ABSTRACT:2,3,4,5,6-Pentafluorobenzonitrile (PFBN) is a valuable intermediate and it is available as a commercial product. In this paper, synthesis and characterization of novel fluorinated poly(ether nitrile)s (PEN) derived from PFBN is reported. Novel fluorinated PENs containing fluorine atoms in the main chain and pendant phenoxy group (2F-PEN) are synthesized by aromatic nucleophilic substitution reaction, of which M0 ranges from 1.77 X 10 4 to 5.16 X 104. The obtained PENs show excellent solubilities in common solvents, and 2F-PEN(6FBA) and 2F-PEN(DPE) can be cast as tough transparent films. These polymers have high thermal stabilities with the 5% weight loss temperature in the range 509-5620C and the Tg of 142-235°C, which is highly dependent on the structures.KEY WORDS Poly(ether nitrile) / Fluorine-Containing Polymer I 2,3,4,5,6-Pentafluorobenzonitrile / Nucleophilic Aromatic Substitution/ Thermal Stability/ High Tg I Solubility/ The high-performance fluorinated polymers have been receiving considerable attention as interesting advanced materials for applications as films, coatings for optical and microelectronics devices, gas separation membranes and so on. 1 -3 The incorporation of fluorine atoms into polymer chains leads to polymers with increased solubility, flame resistance, thermal stability and glass transition temperature, while also leading to decreased color, crystallinity, dielectric constant and moisture absorption. Owing these advantages, poly(aryl ether ketone)s (PEK) containing hexafluoroisopropylidene units had been prepared and studied for use in aerospace and electronic applications. 4 Recently, PEKs containing 2,3,5,6-tetrafluoro-l,4-phenylene moieties were synthesized from perfluorobenzophenone. 5 2,3,4,5,6-Pentafluorobenzoic acid (PFBA) is a valuable intermediate for pharmaceuticals, pesticides, perfumes, cosmetics and so on, and it is available as a commercial product. The authors had reported the synthesis and characterization of novel fluorinated PEKs containing 2,3,5,6-tetrafluoro-1,4-phenylene moieties derived from PFBA. 6 • 7 These fluorinated PEKs showed excellent thermal stability and solubility into common organic solvents. Moreover, the films of these PEKs possess outstanding transparency and low dielectric constants. Therefore they are expected to use a optical and electronic materials and the application study is currently underway.2,3,4,5,6-Pentafluorobenzonitrile (PFBN) is a raw material of PFBA and its commercial availability is much higher than PFBA. 2,6-Difluorobenzonitrile is commonly used as a monomer for poly(ether nitrile)s (PEN) 8 and other types of fluorinated PENs had been previously synthesized from 2,4,5,6-tetrafluoroisophthalonitrile and bisphenols by interfacial polycondensation. 9 However, polymers derived from PFBN have not be reported 290 to our knowledge. In this paper, synthesis and characterization of novel fluorinated PEN derived from PFBN is reported.

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Synthesis and characterization of fluorinated polyetherketones prepared from decafluorobenzophenone

Cited by 33 publications

References 16 publications

Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction

Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction

Synthesis of Thermally Cross-Linkable Fluorine-containing Poly(aryl ether ketone)s I. Phenylethynyl Terminated Poly(aryl ether ketone)s

Synthesis of Novel Fluorine-Containing Poly(aryl ether nitrile)s Derived from 2,3,4,5,6-Pentafluorobenzonitrile

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Synthesis and characterization of fluorinated polyetherketones prepared from decafluorobenzophenone

Cited by 33 publications

References 16 publications

Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH2‐Mediated Polycondensation Reaction

Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH2‐Mediated Polycondensation Reaction

Synthesis of Thermally Cross-Linkable Fluorine-containing Poly(aryl ether ketone)s I. Phenylethynyl Terminated Poly(aryl ether ketone)s

Synthesis of Novel Fluorine-Containing Poly(aryl ether nitrile)s Derived from 2,3,4,5,6-Pentafluorobenzonitrile

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Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction

Highly Fluorinated Poly(arylene ether ketone) Prepared by a CaH₂‐Mediated Polycondensation Reaction