Triarylamine-enchained semifluorinated perfluorocycloalkenyl (PFCA) aryl ether polymers

A variety of perfluorocycloalkenyl (PFCA) aryl ether monomers and polymers with enchained triarylamine units were successfully synthesized, characterized and reported here. These polymers are highly thermally stable and show variable thermal properties. Successful conversion of the newly synthesized TAA enchained perfluorocyclopentenyl (PFCP) aryl ether polymers via formylation and EAS demonstrates the synthetic versatility of TAA moiety and provides an excellent option for application specific post polymerization reactions. The cross-linking behavior of PFCP aryl ether polymers was studied under different reaction conditions. The combination of processability, thermal stabilities, and tailorability makes these polymers suitable for a wide variety of applications including electro-optics, proton exchange membranes and super-hydrophobic applications.

Due to their high crystalline nature, high melting point and the low solubility problem, the processability of these fluoropolymers is difficult. The modification of these fluoropolymers to high performance materials without melt and solution processing limitations demands high cost. There is always a constant demand for fluoropolymers with cheaper feed stocks, variable thermal properties and excellent properties. Although, majority volume of fluoropolymers is derived via chain growth polymerization of fluorinated olefin monomers, step growth polymerization methodology also has been used. Perfluorocyclobutyl (PFCB) aryl ether polymers and fluorinated arylene vinylene ether (FAVE) polymers are two such classes, synthesized via step growth polymerization of aromatic trifluorovinyl ether (TFVE) monomers (Scheme 1). [20][21][22][23][24] The aromatic backbones in these semifluorinated polymers not only address the performance issue, but also provide a means for facile modification to achieve modular utility.
PFCB aryl ether polymers are first synthesized and investigated by The Dow Chemical Company in the early 1990s as potential dielectric materials for integrated circuits applications [20]. PFCB aryl ether polymers are prepared via [2 ? 2] thermo-cyclodimerization reaction of TFVE monomers at reaction temperature of 150-200°C (Scheme 1a). The cycloaddition results in stereo-random PFCB rings in primarily 1,2 fashion (i.e., head-to-head). These uniquely amorphous polymers demonstrate excellent solution processability, modular utility, comparable properties with the highly-market fluoropolymers and high performance in a variety of applications including electro-optics, fuel cell membranes, etc. [21,25].
In 2006, our research group extended TFVE monomer chemistry and introduced a new class of fluoropolymers, namely, fluorinated arylene vinylene ether (FAVE) polymers, derived from the step-growth polycondensation of TFVE monomers with bisphenols (Scheme 1b) [22,23]. FAVE polymers are telechelic in nature and possess dual functionalities, which facilitate chain extension (via thermal [2 ? 2] cyclodimerization of end groups) and tandem cross-linking (due to internal olefins) to polymeric network without the use of any cross-linker additives [23]. The content of internal fluoro-olefin moieties depends on the reaction conditions and can be manipulated on the requirement [22,26].

Results and discussion
Step-growth polymers: methodology PFCP aryl ether polymers and PFCH aryl ether polymers are synthesized via step-growth polymerization of commercially available bisphenols with octafluorocyclopentene (OFCP) and decafluorocyclohexene (DFCH), respectively (Scheme 2) [27,28]. In optimized reaction condition, the bisphenols are mixed with perfluorocycloalkene (PFCA) monomers in a stoichiometric ratio of 1:1 and heated at 80°C in the presence of a base, triethylamine. This method produces PFCA aryl ether polymers with enchained perfluoro-olefin moieties intact, in good yield.
Nucleophilic attack on a perfluoro-olefin is a well studied and documented organofluorine transformation and continues to attract attention periodically [30]. Here, attack on PFCA ring by phenoxide ion, resulted in situ due to action of base on bisphenol, generates a carbanion on perfluorocycloalkene ring which, theoretically, can eliminate fluoride ion resulting in allyl and vinyl substituted products (Scheme 3). However, as the literature demonstrates, the ratio of vinyl to allyl substituted products varies and depends on the PFCA ring size, nucleophilicity of attacking anion, and reaction conditions. [28,31,32].

Synthesis and characterization
PFCP aryl ether polymers derived from the OFCP gave exclusively vinyl fluoro-olefin enchainments, no trace of allyl product was noticed [27]. However, the PFCH aryl ether polymers prepared from DFCH gave both, vinyl fluoroolefins as major and allyl fluoro-olefins as minor enchainments via a double addition-elimination mechanism [28].
Gel permeation chromatography (GPC) showed number-average molecular weights (M n ) from 9,100 to 15,400 for PFCP aryl ether polymers derived from different bisphenols [27]. In case of PFCH aryl ether polymers, M n ranged from 9,400 to 15,600 [28]. Thermogravimetric analysis (TGA) showed excellent thermal stability of these polymers. The degradation temperature at 5 % weight loss (T d 5 %) varied from 432 to 483°C and 383 to 444°C for PFCP aryl ether polymers and PFCH aryl ether polymers, respectively. Thermal analysis via differential scanning calorimetry (DSC) showed variable glass transition temperature (T g ) ranging from 432 to 483°C and 90 to 132°C for PFCP aryl ether polymers and PFCH aryl ether polymers, respectively. Interestingly, both PFCA aryl ether polymers synthesized from Bisphenol-AF also showed melting peaks in their respective DSC thermogram. This anomalous crystalline nature was attributed to a higher fluorine content, as found with -C(CF 3 ) 2 moiety of the bisphenol-AF group [33].
In this manuscript, PFCP aryl ether monomer and polymers with enchained triarylamine (TAA) units were synthesized and studied (Scheme 4, 5). The latent reactivity of TAA unit provides the post polymerization modification opportunities to achieve application specific properties Scheme 6.
The polymerization of M with different bisphenols, in the presence of base, triethylamine, and reaction temperature of 80°C, yields a variety of copolymers with alternating architectures (Scheme 5). Polymers P1-P3 were obtained in good yield ([70 %) and characterized via, 1 H NMR, 19 F NMR, GPC, TGA and DSC techniques (Table 1). 19 F NMR spectra show the uniform vinyl linkage along the polymer chain and supports the concept of double addition-elimination reaction on OFCP rings which leave the double bond intact. A small 19 F NMR signal around -150 ppm was observed for polymer P3 indicating the presence of a trace amount of allyl substitution along the polymer chain (Figs. 2, 3s, 5s). Thermal stabilities for these polymers studied via TGA analysis. The decomposition temperature (T d at 5 % weight loss, in nitrogen atmosphere) ranges from 370 to 456°C (Fig. 3). The impressive degradation temperatures (T d 5 %) up to 450°C are typical for PFCP aryl ether polymer systems [27]. Thermal analysis via differential scanning calorimetry (DSC) shows the polymers show variable glass transition temperature (T g ) depending on the bisphenol used. The T g for these polymers ranges from 87 to 106°C (Fig. 4). There was no sign of melting peak, as expected.
Post-polymerization functionalization [e.g. chromophorization-synthesizing an electro-optic (EO) chromophore incorporated aldehyde (P4) can be further modified into a range of application-specific molecules, including extension into an EO chromophore, hole-transport and photovoltaic materials [29,34,36,37]. EAS reaction on these PFCP aryl ether polymers demonstrates the accessibility of these TAA moieties for further post polymerization modifications, which extends the overall versatility of this polymeric system.   extent of cross-linking and reaction conditions are warranted.

(b) Free radical cross-linking
Cross-linking efforts using free radical initiators including AIBN and lauroyl peroxide did not work. As the literature suggests, perfluorocyclic-olefins do not homopolymerize under radical conditions [38]. Therefore, electron deficiency factor combined with steric hindrance factor inhibits the crosslinking of these PFCP polymers via free radical mechanism.
(c) Ionic cross-linking The PFCP polymers keep the cyclic olefin intact. The literature suggests, in suitable conditions, multiple nucleophilic substitutions on PFCP ring are possible [39]. Model reactions also support the multiple substitutions on PFCP rings (Scheme 7).
Model compound 1,2-diphenyl perfluorocyclopentenyl ether (1) shows two clean signals, corresponding to two kinds of fluorine atoms in a symmetric environment, as expected (Fig. 6a). When the sodium phenoxide reacts with (1), 19 F NMR shows vinyl fluorine signal at 158.6 ppm confirming the third substitution (Fig. 6b). This vinyl fluorine signal goes away with further reaction of (2) with the phenoxide ion. Initial studies show PFCP aryl ether polymers react with dinucleophiles, undergo cross-linking in different reaction conditions and give insoluble products (Scheme 8). Various parameters, including different reaction conditions and different dinucleophiles are under study.

Materials and instrumentation
Octafluorocyclopentene and decafluorocyclohexene were purchased from SynQuest Laboratories, while all other chemicals were purchased from Alfa Aesar. Commercially purchased chemicals were used as purchased unless otherwise stated. All synthesized polymers P1-P5 were characterized by 1 H and 19 F NMR Spectroscopy, Gel permeation chromatography (GPC), Thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC) techniques. NMR Spectroscopy was performed on Bruker advanced IIITM 500 MHz spectrometer. Chemical shifts were reported in ppm (d) with reference to deuterated acetone (2.09 ppm) and trichlorofluoromethane (0 ppm) for 1 H and 19 F NMR, respectively. GC-MS was obtained on Shimadzu GCMS solution. Analytical thin layer chromatography was performed on EM reagents 0.25 mm silica gel 60-F plates. Molecular weight  measurements were performed on gel permeation chromatography (Viscotek GPCmax, VE2001) system equipped with a Viscotek TDA 302 Triple Array Detector and two ViscoGEL I-Series (I-MBHMW 3078, Viscotek) columns in series. THF was used as eluent and polystyrene standards were used for calibration. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy was done on a Thermo-Nicolet Magna 550 FIR spectrophotometer with a high endurance diamond ATR attachment. DSC analysis was performed on a Mettler Toledo DSC 1 system in the nitrogen atmosphere with heating and cooling rate of 10 C/min. The T g of polymers were measured from the third heating cycle using Star-E version 10.0 software suite. The thermal stability measurements were performed on a Mettler Toledo TGA/DSC 1 LF instrument, in the nitrogen atmosphere with a heating rate of 10 C/min.

Synthesis of monomer (M)
In a flame dried 50 ml single necked round bottom flask, equipped with a magnetic stirrer, 3.84 mmol of bis(4hydroxyphenyl)phenylamine (B), 9.60 mmol of triethylamine and 6 ml of anhydrous DMF were introduced. The solution was purged with nitrogen for 10 min. The solution was heated at 65°C for 2 h. Let the reaction mixture cooled down to room temperature. This reaction mixture was added to a 6 ml DMF solution containing 9.60 mmol of octafluorocyclopentene, in a 100 ml single necked flask equipped with stirrer, dropwise with a syringe. The solution was stirred at room temperature for next 12 h. Further, the reaction was heated at 65°C for the next 2 h to ensure the completion of the reaction. The solution was then cooled down, and the pure product was isolated by column chromatography with pure hexane, as eluent, to give white product (yield = 71 %). 1

Conclusion
We have developed a step-growth polymerization of bisphenols with PFCA towards synthesis of a new class of PFCA aryl ether polymers from commercial feedstock. PFCA aryl ether polymers can be easily modified and functionalized using bisphenols with different spacer functional groups. PFCA aryl ether polymers exhibited very interesting thermal properties with variable T g depending upon the chosen bisphenol. These polymers were obtained in good yields and show high thermal stabilities under nitrogen atmosphere. Successful conversion of the newly synthesized TAA enchained PFCP aryl ether polymers via formylation and EAS demonstrated the synthetic versatility of TAA moiety and provides an excellent option for application specific post polymerization reactions. PFCP aryl ether polymers with biphenyl units also demonstrate cross-linking behavior upon thermal activation. Exact mechanistic details for this thermal cross-linking are still unknown and further investigations are warranted. Also, PFCP aryl ether polymers undergo ionic cross-linking upon treatment with strong dinucleophiles.
Future studies include the mechanistic studies on the cross-linking behavior of PFCA aryl ether polymers, full chromophorization on TAA units of these successfully