perfluorocyclopentenyl (pfcp) aryl ether polymers via polycondensation of octafluorocyclopentene...

Perfluorocyclopentenyl (PFCP) Aryl Ether Polymers viaPolycondensation of Octafluorocyclopentene with BisphenolsJean-Marc Cracowski,† Babloo Sharma,‡ Dakarai K. Brown,† Kenneth Christensen,† Benjamin R. Lund,‡

and Dennis W. Smith, Jr.*,‡

†Department of Chemistry, School of Material Science and Engineering and Center for Optical Materials Science and EngineeringTechnologies (COMSET), Clemson University, Clemson, South Carolina 29634, United States‡Department of Chemistry and The Alan G. MacDiarmid NanoTech Institute, The University of Texas at Dallas, Richardson,Texas 75080, United States

ABSTRACT: A unique class of aromatic ether polymerscontaining perfluorocyclopentenyl (PFCP) enchainment wasprepared from the simple step growth polycondensation ofcommercial bisphenols and octafluorocyclopentene (OFCP)in the presence of triethylamine. Model studies indicate thatthe second addition/elimination on OFCP is fast and poly-condensation results in linear homopolymers and copolymerswithout side products. The synthesis of bis(heptafluoro-cyclopentenyl) aryl ether monomers and their condensationwith bisphenols further led to PFCP copolymers with alternating structures. This new class of semifluorinated polymers exhibitsurprisingly high crystallinity in some cases and excellent thermal stability.

■ INTRODUCTIONFluoropolymers exhibit outstanding thermal stability, chemicalresistance, unique surface properties, low refractive index, andlow dielectric constant.1−5 Despite their general limitedsolution and melt processability, emerging technologiescontinue to drive the incorporation of fluorine into new poly-meric systems due to their unique combination of pro-perties. Here we report the polycondensation of commercialoctafluorocyclopentene (OFCP) and commercial bisphenols togive a new class of semifluorinated aromatic ether polymers(Scheme 1).

Although, by far, the largest volume of fluoropolymers areaccessed by chain growth polymerization of fluorine-containingolefins, step growth mechanisms have also been established. Inparticular, Babb and co-workers6 at Dow Chemical introduceda new class of semifluorinated perfluorocyclobutyl (PFCB) arylether polymers prepared from thermal cyclopolymerization ofaromatic trifluorovinyl ether (TFVE) monomers (Scheme 2a).These PFCB polymers, investigated as potential dielectricresins for integrated circuits at Dow and later for nextgeneration optical applications by others,5 are uniquelyamorphous due to their stereorandomness and exhibit excellent

processability, high thermal stability, and tunable opticalproperties.5,8

More recently, a new class of semifluorinated polymer wasdeveloped from the nucleophilic addition of bisphenols andaromatic TFVE monomers to give fluorinated arylene vinyleneether (FAVE) polymers (Scheme 2b).9−11 The new FAVEpolymers exhibit similar advantageous properties to PFCBwhile offering more cost-effective functional diversity sinceboth aromatic TFVE monomers and functional bisphenols arecommercially available or easily prepared. Further, FAVE

Received: November 7, 2011Revised: December 1, 2011Published: December 22, 2011

Scheme 1. Perfluorocyclopentenyl (PFCP) Aryl EtherPolymer Synthesis

Scheme 2. (a) Synthesis of PFCB Polymer and (b) FAVEPolymer from TFVE Monomers

Article

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© 2011 American Chemical Society 766 dx.doi.org/10.1021/ma2024599 | Macromolecules 2012, 45, 766−771

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polymers containing fluorinated vinyl groups are found to bepotentially reactive and thermally cross-linkable.Octafluorocyclopentene (OFCP) is a readily available

perfluorocyclic olefin with unique chemistry. Many studieshave been reported on the reaction of OFCP with nucleophiles,such as phenoxides,12−15 arenethiolates,16 amines,17−19 eno-lates, phosphonium ylides,20 and organolithium reagents.20−22

Many other examples include OFCP derivatives for photo-chromic applications.23−25 There are very few examples ofpolymers of perfluorocyclopentene by traditional chain growthmechanisms. This perfluorocyclic olefin does not homopoly-merize under radical conditions,26 and radical copolymeriza-tions with styrene and vinyl acetate lead to copolymers with avery low molar ratio of perfluorocyclopentene.27 Nevertheless,copolymerization with electron-rich monomers like vinyl ethersleads to alternating copolymers.26,27 Step growth polymer-ization of OFCP with bis(silyl) ethers was reported, but theresulting polymers exhibited low molecular weight.28 To ourknowledge, the polycondensation of bisphenols with perfluoro-cycloolefins has not been previously reported.

■ RESULTS AND DISCUSSIONPrior to polycondensation, a model reaction was performedusing OFCP and sodium phenoxide (Scheme 3). Interestingly,

75% of the clean product mixture was the bis adduct asdetermined by 19F NMR spectroscopy, most likely due toincreased solubility of the monoadduct (Figure 1).

Polycondensation was attempted using the sodium salt ofbis(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF)and OFCP in DMF at 80 °C for 10 h. Low-molecular-weightoligomers were obtained. Thus, an alternative method wasexplored using triethylamine as the base (Scheme 1) to affordperfluorocyclopentenyl (PFCP) aryl ether homopolymer P1 ofnumber-average molecular weight and PDI of 9100 g mol−1 and2.5, respectively (Table 1).Moreover, homopolymer P1 was determined to be

hydroxytelechelic by the absence of 19F NMR signals centeredat −149 ppm representative of the fluoroolefin (Figure 2b).

In the 1H NMR spectrum (Figure 2a), there are two signalsrepresenting aromatic (6.9 and 7.3 ppm) protons, as expected.These signals (dd, J = 8.8 Hz) indicate a symmetric environ-ment around both ether linkages of the PFCP rings andsupport an addition−elimination reaction which leaves thedouble bond of the PFCP ring intact. Further, 19F NMR showsthree clean signals, corresponding to three unique fluorineatoms in symmetrical environments, as expected (Figure 2b). APFCP end-capped polymer was also prepared by the additionof an excess of OFCP at the end of the reaction.PFCP aryl ether homopolymer P2 was prepared from

Bisphenol A via the same methodology as P1 (Scheme 1). Forhomopolymer P2, the number-average molecular weight andPDI were 9600 and 1.15 after 24 h reaction time (Table 1).Homopolymer P2 was characterized by 1H NMR and19F NMR spectroscopy and, as before, exhibited a cleanaddition−elimination polycondensation (Figure 3). 1H NMRshows symmetric aromatic groups and a clean singlet for themethyl protons (1.57 ppm). 19F NMR shows only tworesonances corresponding to the PFCP ring substituted in asymmetrical fashion.PFCP aryl ether homopolymer P3 was prepared from

biphenol under similar conditions (Scheme 1). P3 shows a

Scheme 3. Model Reaction between OFCP and SodiumPhenoxide

Figure 1. 19F NMR spectrum of the model reaction product mixture.

Table 1. PFCP Polymers Molecular Weight, PolydispersityIndex (PDI), Thermal Properties, and Yield ofPolymerization

PFCP Mn Mw PDIa Tg (°C)b

Td5%(°C)c

yield(wt %)

homopolymer P1 9100 22900 2.5 124 483 70homopolymer P2 9600 11100 1.1 89 432 54homopolymer P3 15450 29800 1.9 105 460 90P3-co-P1d 5900 9300 1.5 94 325 74copolymer (M1-alt-BP) 8400 14500 1.7 98 310 69copolymer (M2-alt-6F) 2000 3000 1.5 68 224 51aGPC in THF using polystyrene as standard after precipitation inmethanol. bDSC (heating rate 10 °C/min) in a nitrogen atmosphere.cTGA (heating rate 10 °C/min) in a nitrogen atmosphere. d0.49/0.51molar ratio of monomer 1/2 in copolymer as determined by 19F NMRspectroscopy.

Figure 2. (a) 1H NMR and (b) 19F NMR of PFCP aryl etherhomopolymer P1.

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higher number-average molecular weight of 15 450, with a PDIof 1.9 (Table 1), relative to the above-mentioned homopoly-mers (P1 and P2), with clean and well-integrated signals in1H NMR and 19F NMR spectroscopy (Figure 4).

1H and 19F NMR spectra show no evidence of chiral carbonatoms within the cyclopentene ring as would be expected in thecase of an addition rather than an addition−eliminationreaction. PFCP homopolymers (P1, P2, and P3) showabsorption in the ultraviolet spectrum (λmax 210 nm for P1,P2 and 260 nm for P3) with no corresponding fluorescence.

Thermal analysis of these polymers shows unexpectedproperties (Table 1). P1 exhibits a glass transition temperature(Tg) of 124 °C, as determined by DSC, and a polymorphiccrystallization and melting at ca. 218 and 250 °C, respectively(Figure 5a). The decomposition temperature (Td) at 5% weight

loss determined by thermogravimetric analysis (TGA) underN2 was 483 °C for P1 with a number-average molecular weightof 9100 (Figure 6). Remarkably, homopolymer P1 exhibited anexceptional char yield of greater than 85% up to 800 °C.DSC thermograms for P2 exhibited a glass transition temper-

ature of 89 °C. However, unlike P1, PFCP polymer P2 does notshow crystallinity under these conditions (Figure 5b), presumablydue to the decreased fluorine content as analogously observed forthe 6F-PFCB polymer.29 TGA analysis under a N2 atmosphereshows that the decomposition temperature (Td) at 5% weightloss exceeds 430 °C (Figure 6).

Figure 3. (a) 1H NMR and (b) 19F NMR of PFCP aryl etherhomopolymer P2.

Figure 4. 1H NMR and 19F NMR of PFCP aryl ether homopoly-mer P3.

Figure 5. DSC thermograms of PFCP aryl ether homopolymer (a) P1,(b) P2, and (c) P3.



PFCP aryl ether homopolymer P3 exhibited an endothermictransition determined by DSC of 105 °C (Figure 5c). Like P2and unlike P1, P3 does not show crystallinity or meltingbehavior under these conditions (Figure 5c). This highermolecular weight homopolymer P3 gave decompositiontemperature of 460 °C (Td at 5% weight loss, Figure 6).A random PFCP copolymer was also prepared in one step

with bisphenols and OFCP (Table 1). Reactions of variablebisphenols with a slight excess of OFCP led to novel bis-(heptafluorocyclopentenyl) aryl ether monomers (M1, M2)and their step growth polymerization with other bisphenolsafforded PFCP copolymers with alternating arylene etherstructures (Scheme 4).

As seen earlier, biphenol gave higher molecular weight thanBisphenol AF during polymerization with OFCP (P3 vs P1).This may be due to the electron-withdrawing effect of the CF3groups decreasing its nucleophilicity compared to biphenol.Likewise, alternating copolymers of 6F containing monomerM1 gave the highest molecular weight for identical copolymerstructures of different monomers (Table 1). This methoddemonstrates a modular approach to alternating copolymersfrom monomers of variable reactivity. Further, because of itshigher molecular weight, copolymer M1-alt-BP exhibits morerobust thermal properties than copolymer M2-alt-6F.

■ CONCLUSIONWe have developed a step growth polymerization of bisphenolswith OFCP toward synthesis of a new class of perfluorocyclo-pentenyl (PFCP) aryl ether polymers from commercial

feedstocks. PFCP polymers can be easily modified and func-tionalized by using bisphenols with different spacer functionalgroups. PFCP polymers exhibited very interesting thermalproperties with variable Tg depending upon the chosenbisphenol. These polymers were obtained in good yields andshow high thermal stabilities under N2 with Td at 5% weightloss ranging from 432 to 483 °C for homopolymers and 224 to325 °C for copolymers. This new family of semifluorinated arylether polymers can easily have phenolic or perfluorocyclopen-tenyl terminal groups depending on the stoicheometry of thereactants. Further, PFCP polymers contain main chain vinylether groups for postpolymerization modification and potentialcross-linking.

■ EXPERIMENTAL SECTIONChemical Reagents. Octafluorocyclopentene (99%) was pur-

chased from Synquest Laboratories and used as received. Bis-(hydroxyphenyl)hexafluoroisopropylidene (Bisphenol AF) and 4,4′-biphenol were donated by Tetramer Technologies, L.L.C., Pendelton,SC. Deuterated solvents were purchased from Mallinckrodt ChemicalsInc. All other chemicals and solvents (analytical grade) were purchasedfrom Sigma-Aldrich and used as received unless otherwise stated.

Instrumentation. M1 andM2 and copolymers were characterizedon a JEOL ECX-300 MHz NMR spectrometer via 1H, 19F, andproton-fluorine decoupled 13C spectroscopy. P1, P2, and P3 werecharacterized on a Bruker 400 MHz NMR spectrometer via 1H, protondecoupled 19F, and proton decoupled 13C spectroscopy. Chemicalshifts were measured in ppm (δ) with reference to internaltetramethylsilane (0 ppm), deuterated chloroform (77 ppm)/deuterated tetrahydrofuran (25.3 ppm)/deuterated acetone (29.8ppm), and trichlorofluoromethane (0 ppm) for 1H, 13C, and 19F NMR,respectively. For coupled spectra, values are reported from the centerof the pattern. Attenuated total reflectance Fourier transform infrared(ATR-FTIR) analyses of neat samples were performed on a Thermo-Nicolet Magna 550 FTIR spectrophotometer with a high endurancediamond ATR attachment. Ultraviolet−visible absorption and fluore-scence spectroscopy were measured in THF on an Agilent 8453 UV−vis spectroscopy system and Perkin-Elmer LS 50 B luminescencespectrometer, respectively. Differential scanning calorimetry (DSC)analysis was performed on a Mettler Toledo DSC 1 system in nitrogenat a heating rate of 10 °C/min. The glass transition temperature (Tg)was obtained from a second heating cycle using Star E version 10.0software suite. Thermal gravimetric analysis (TGA) was performed ona Mettler-Toledo TGA/DSC 1 LF instrument in nitrogen at a heatingrate of 10 °C/min up to 800 °C. Molecular weights for polymers P1,P2 and P3 were measured by size exclusion chromatography (SEC)analysis on a Viscotek VE 3580 system equipped with a ViscoGELcolumn (GMHHR-M), connected to a refractive index (RI) detector.GPC solvent/sample module (GPCmax) was used with HPLC gradeTHF as the eluent and calibration was based on polystyrene standards.For copolymers, gel permeation chromatography (GPC) data werecollected in THF from a Waters 2690 Alliance System with photo-diode array detection. GPC samples were eluted in series throughPolymer Laboratories PLGel 5 mm Mixed-D and Mixed-E columns at35 °C. Molecular weights were obtained using polystyrene as astandard (Polymer Laboratories Easical PS-2).

Synthesis of PFCP Aryl Ether Homopolymer P1. In a 25 mLSchlenk tube equipped with a magnetic stirrer was added 1.00 g(2.97 mmol) of Bisphenol AF, 0.662 g (6.54 mmol) of triethylamine,and 10 mL of DMF. The solution was degassed with nitrogen for10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentene was addedvia syringe; the Schlenk flask was heated slowly to 80 °C for 24 h. Thepolymer was then precipitated in 100 mL of methanol, filtered, washedseveral times with methanol, and dried under vacuum at 50 °C for24 h, giving 1.1 g of a white powder (yield = 74%). 1H NMR(400 MHz, THF-d8, δ): 6.91 (dm,

3JH‑2(H‑1) = 8.80 Hz, 4H), 7.32 (dm,3JH‑1(H‑2) = 8.80 Hz, 4H). 19F NMR (376 MHz, THF-d8, δ): −63.85(6F), −115.13 (4F), −130.17 (2F). 13C NMR (100 MHz, THF-d8, δ):

Figure 6. TGA thermograms of PFCP aryl ether homopolymers P1,P2, and P3.

Scheme 4. Bis(heptafluorocyclopentenyl) Aryl EtherMonomers Synthesis and Polymerization



64.6, 110.8 (PFCP, CF2), 113.8 (PFCP, CF2), 117.5, 125.2, 130.8,132.7, 134.9 (PFCP, CC), 155.2. FTIR (ν, cm−1): 3150 and 3063(H−CC), 1274 (C−O), 1151 (C−F), 780 and 658 (C−F).Synthesis of PFCP Aryl Ether Homopolymer P2. Homopol-

ymer P2 was synthesized using the same method as P1, except it wasprecipitated in a 0.5/0.5 volume ratio of water/methanol and washedseveral times with a solution of 0.5/0.5 volume ratio of water/methanol, giving a white powder after drying (yield = 90%). 1H NMR(400 MHz, acetone-d6, δ): 1.51 (dm, 6H), 6.69 (dm, 3JH‑2(H‑1) = 8.91Hz, 4H), 7.08 (dm, 3JH‑1(H‑2) = 8.91 Hz, 4H). 19F NMR (376 MHz,acetone-d6, δ): −114.20 (4F), −129.71 (2F). 13C NMR (100 MHz,THF-d8, δ): 31.0, 42.7, 110.6 (PFCP, CF2), 114.1 (PFCP, CF2), 117.1,128.5, 134.8 (PFCP, CC), 147.8, 153.0. FTIR (ν, cm−1): 3130 and3065 (H−CC), 1272 (C−O), 1142 (C−F), 782 and 654 (C−F).Synthesis of PFCP Aryl Ether Homopolymer P3. Homopol-

ymer P3 was synthesized using the same method as P2, except thereaction time was 36 h, giving a white powder after drying (yield =50%). 1H NMR (400 MHz, acetone-d6, δ): 6.92 (dm, 3JH‑2(H‑1) = 8.58Hz, 4H), 7.31(dm, 3JH‑1(H‑2) = 8.58 Hz, 4H). 19F NMR (376 MHz,acetone-d6, δ): −113.89 (4F), −129.60 (2F). 13C NMR (100 MHz,acetone-d6, δ): 110.5 (PFCP, CF2), 114.0 (PFCP, CF2), 118.5, 128.8,135.0 (PFCP, CC), 137.7, 154.5. FTIR (ν, cm−1): 3151 and 3070(H−CC), 2941 (C−H), 1270 (C−O), 1150 (C−F), 780 and 653(C−F).Synthesis of P3-co-P1. In a 25 mL Schlenk tube equipped with a

magnetic stirrer was added 0.793 g (2.36 mmol) of Bisphenol AF,0.439 g (2.36 mmol) of biphenol, 1.052 g (10.39 mmol) oftriethylamine, and 10 mL of DMF. The solution was degassed withargon for 10 min, and 0.631 g (2.97 mmol) of octafluorocyclopentenewas added via syringe; the Schlenk flask was heated at 80 °C for 10 h.The dissolved polymer was then precipitated in 100 mL of 0.5/0.5volume ratio of water/methanol and washed several times with asolution of 0.5/0.5 volume ratio of water/methanol and dried undervacuum at 50 °C for 24 h, giving 1.7 g of a white powder (yield =74%). 1H NMR (300 MHz, acetone-d6, δ): 7.15 (m). 19F NMR (282MHz, acetone-d6, δ): −64.44 (m, 3F), −115.21 (m, 4F), −130.61 (m,2F). FTIR (ν, cm−1): 3150 and 3075 (H−CC), 1273 (C−O), 1150(C−F), 787 and 661 (C−F).Synthesis of M1. To a 50 mL round-bottom flask equipped with

a magnetic stirrer were introduced 2.00 g (5.95 mmol) of BisphenolAF, 2.77 g (13.1 mmol) of triethylamine, and 20 mL of DMF, and thesolution was degassed with argon for 10 min. 2.775 g (13.09 mmol) ofoctafluorocyclopentene was then introduced with a syringe, and thesolution was heated slowly to 80 °C for 10 h. The solvent was thenremoved, and the crude product was isolated by columnchromatography in dichloromethane (Rf = 0.93) to give 3.1 g of acolorless oil (yield = 65%). 1H NMR (300 MHz, CDCl3, δ): 7.19(d, 3JH‑1(H‑2) = 8.58 Hz, 4H), 7.43 (d, 3JH‑1(H‑2) = 8.58 Hz, 4H).19F NMR (282 MHz, CDCl3, δ): −63.91 (s, 6F), −115.32 (d, 3JF1(F‑2) =9.84 Hz, 4F), −115.65 (d, 3JF‑1(F‑2) = 13.11 Hz, 4F), −129.39 (s, 4F),−146.61 (s, 2F). 13C NMR (75 MHz, CDCl3, δ): 67.4, 105.5, 109.1,111.1, 112.0, 118.3, 123.9, 131.3, 131.7, 138.0, 154.1. FTIR (ν, cm−1):3150 and 3075 (H−CC), 1270 (C−O), 1160 (C−F), 783 and 665(C−F). GC-MS (m/z) [M + H]+: 720.4 Elemental analysis: Calcd(Found) C = 41.69 (41.62), H = 1.12 (1.03), F = 52.75 (53.03).Synthesis of M2. M2 was synthesized and isolated with the same

method as described for M1 (Rf = 0.86 in dichloromethane) to give awhite solid (yield = 69%). 1H NMR (300 MHz, CDCl3, δ): 7.25 (dm,3JH‑1(H‑2) = 8.61 Hz, 4H), 7.59 (d, 3JH‑1(H‑2) = 8.61 Hz, 4H). 19F NMR(282 MHz, CDCl3, δ): −115.32 (m, 4F), −115.36 (m, 4F), −129.36(s, 4F), −148.85 (s, 2F). 13C NMR (75 MHz, CDCl3, δ): 104.3, 111.4,114.1, 118.1, 122.2, 130.2, 131.2, 131.9, 153.9. FTIR (ν, cm−1): 3133and 3074 (H−CC), 1272 (C−O), 1145 (C−F), 787 (C−F). GC-MS (m/z) [M + H]+: 570.3 Elemental analysis: Calcd (Found) C =46.33 (46.36), H = 1.41 (1.36), F = 46.64 (46.70).Synthesis of Copolymer (M1-alt-BP). To a 25 mL Schlenk tube

equipped with a magnetic stirrer was added 0.500 g (0.694 mmol) ofM1, 0.129 g (0.694 mmol) of biphenol, 0.155 g (1.53 mmol) oftriethylamine, and 5 mL of DMF. The solution was degassed withargon for 10 min, and the Schlenk tube was heated slowly to 80 °C for

10 h under stirring. The dissolved polymer was then precipitated in100 mL of 0.5/0.5 volume ratio of water/methanol and washed severaltimes with a solution of 0.5/0.5 volume ratio of water/methanol,giving a white powder after drying (yield = 51%). 1H NMR (300 MHz,acetone-d6, δ): 6.88 (m, 8H), 7.15 (m, 4H), 7.35 (m, 4H). 19F NMR(282 MHz, acetone-d6, δ): −64.45 (m, 3F), −115.02 (m, 4F), −130.6(m, 2F). FTIR (ν, cm−1): 315 and 3090 (H−CC), 2941 (C−H),1265 (C−O), 1150 (C−F), 790 and 658 (C−F).

Synthesis of Copolymer (M2-alt-6F). The copolymer wasprepared using the same method as copolymer M1-alt-BP, giving awhite powder after drying (yield = 69%). 1H NMR (300 MHz,acetone-d6, δ): 6.72 to 7.19 (m, 8H), 7.26 to 7.45 (m, 8H). 19F NMR(282 MHz, acetone-d6, δ): −64.18 (m, 3F), −115.37 (m, 4F), −130.54(m, 2F). FTIR (ν, cm−1): 3130 and 3103 (H−CC), 2960 (C−H),1263 (C−O), 1145 (C−F), 785 (C−F).

■ AUTHOR INFORMATIONCorresponding Author*E-mail: [email protected].

■ ACKNOWLEDGMENTSThe authors thank Defense Advanced Research ProjectsAgency (DARPA) for funding and Tetramer TechnologyLLC for the gift of bisphenols. We also thank the Robert A.Welch Foundation (Grant AT-0041), Intel Corporation, andThe University of Texas at Dallas for partial support.

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