¹H NMR, ¹³C NMR and ¹⁹F NMR spectra were recorded on a Varian spectrometer at 300, 75 and 300 MHz, respectively, in deuterated chloroform CDCl₃, N,N-dimethylformamide (DMF-d₇) and dimethylsulfoxide (DMSO- d₆). Tetramethylsilane (TMS) and trifluoroacetic acid (TFA) were used as internal standards, respectively. Glass transition temperatures, T_g, were determined in a DSC-7 Perkin Elmer Inc., at scanning rate of 10˚C/min under nitrogen atmosphere. The samples were encapsulated in standard aluminum DSC pans. Each sample was run twice on the temperature range between 30˚C and 300˚C under nitrogen atmosphere. The T_g values obtained were confirmed by TMA from the first heating cycle conducted at a rate of 10˚C/min under nitrogen atmosphere with a TA Instruments Thermomechanical Analyzer TMA 2940. Onset of decomposition temperature, T_d, was determined using thermogravimetric analysis, TGA, which was performed at a heating rate of 10˚C/min under nitrogen atmosphere with a DuPont 2100 instrument. FT-IR spectra were obtained on a Thermo Nicolet 6700 spectrometer. Molecular weights and molecular weight distributions were determined with reference to polystyrene standards on a Waters 2695 ALLIANCE GPC at 35˚C in tetrahydrofuran using a universal column and a flow rate of 0.5 mL∙min⁻¹. X-ray diffraction measurements of copolymer films as cast were carried out in a Siemens D-5000 diffractometer between 4 and 70 degrees 2θ, at 35 KV 25 mA, using CuK_α radiation (1.54 Å). Tapping mode atomic force microscopy (TM-AFM) was performed in air using a Scanning Probe Microscope Jeol JSPM-4210 with a NSC12 mmasch needle. The samples were imaged at ambient conditions.

Norbornene-5,6-dicarboxylic anhydride (NDA) was prepared via Diels-Alder condensation of cyclopentadiene and maleic anhydride according to literature [6] . 2,3,4,5,6-Pentafluoroaniline, aniline, phenol and sodium 4-hy- droxybenzenesulfonate dihydrate were purchased from Aldrich Chemical Co. and used without further purification. 1,2-Dichloroethane, dichloromethane, p-dioxane, toluene and N,N-dimethylacetamide were dried over anhydrous calcium chloride and distilled over CaH₂. Bis(tricyclohexylphosphine) benzylidene ruthenium(IV) dichloride (I) and ClRh(PPh₃)₃ were purchased from Aldrich Chemical Co. and used as received.

Monomer 2a was synthesized according to the general methodology previously described for the synthesis of aliphatic and aromatic norbornene dicarboximides [8] . Thus, 2,3,4,5,6-pentafluoroaniline reacted with NDA to the corresponding amic acid which was cyclized to imide using acetic anhydride as dehydrating agent (Scheme 1) NDA ( 5.0 g , 30.5 mmol) was dissolved in 40 mL of CH₂Cl₂. An amount of 5.58 g (30.5 mmol) of 2,3,4,5,6- pentafluoroaniline in 20 mL of CH₂Cl₂ was added dropwise to the stirred solution of NDA. The mixture was boiled for 3 h and then cooled to room temperature. Solvent removal gave a white solid of amic acid. The obtained amic acid 1a ( 10.3 g , 29.7 mmol), anhydrous sodium acetate ( 2.50 g , 30.47 mmol) and acetic anhydride ( 21.0 g , 205.7 mmol) were heated at 80˚C for 24 h. The mixture was washed with dilute HCl and ex-tracted into ether. The ether layer was washed with dilute HCl, saturated NaHCO₃ and H₂O. Solvent was evapo-

Scheme 1. Synthesis of N-pentafluorophenyl- and N-phenyl-exo-endo-norbornene-5,6-dicarboximide, 2a and 2b, respectively.

rated and pure monomer 2a was obtained after twice recrystallization from hexane and dried in a vacuum oven at 50˚C overnight: yield = 75%; m.p. = 112˚C - 113˚C; ¹H NMR (300 MHz, CDCl₃), d (ppm) = 6.36 (1H, s), 6.25 (1H, s), 3.53 (1H, s), 3.42 (1H, s), 2.96 (2H, s), 1.70 - 1.54 (2H, m); ¹³C NMR (75 MHz, CDCl₃): d (ppm) = 174.7 (C=O), 147.8 - 139.6 (C-F), 137.8 (C=C), 134.4 (C=C), 107.1 (C-N), 52.1, 48.4, 45.8, 45.6, 42.9; ¹⁹F NMR (300 MHz, CDCl₃, ref. TFA [−77 ppm]): d (ppm) = −142.2, −142.4, −150.1, −150.6, −160.1, −160.4; FT-IR (KBr, cm⁻¹): 3076, 2949 (C-H asym str), 2880 (C-H sym str), 1782 (C=O), 1724 (C=O), 1644 (C=C str), 1519, 1356, 1299 (C-F), 1172, 1157, 984, 793.

Monomer 2b was synthesized according to literature (Scheme 1) [8] [9] . NDA ( 5 g , 30.5 mmol) was dissolved in 50 mL of toluene. An amount of 2.8 g (30.1 mmol) of aniline in 10 mL of toluene was added dropwise to the stirred solution of NDA. The reaction was maintained at 50˚C for 3 h. A precipitate was filtered and dried to give 7.6 g (29.5 mmol) of amic acid 1b. The amic acid obtained ( 7.6 g , 29.5 mmol), anhydrous sodium acetate ( 3.0 g , 36 mmol) and acetic anhydride ( 21 g , 212 mmol) were heated at 90˚C for 6 h and then cooled. The solid crystallized on cooling was filtered, washed several times with water and dried in a vacuum oven at 50˚C overnight. Pure monomer 2b was obtained after twice recrystallization from toluene: yield = 81%; m.p. = 195˚C - 196˚C; ¹H NMR (300 MHz, CDCl₃), d (ppm) = 7.49 - 7.25 (5H, m), 6.33 (2H, s), 6.24 (2H, s), 3.38 (2H, s), 2.84 (2H, s), 1.62 - 1.46 (2H, m); ¹³C NMR (75 MHZ, CDCl₃): d (ppm) = 176.8 (C=O), 137.8 (C=C), 134.4, 131.7 (C-N), 129.0, 128.4, 126.2, 47.7, 45,7, 42.8; FT-IR (KBr, cm⁻¹): 3064, 2946 (C-H asym str), 2877 (C-H sym str), 1770 (C=O), 1594 (C=C str), 1454 (C-N), 1382, 1329, 1289, 1188, 975, 799.

Copolymerizations were carried out in glass vials under dry nitrogen atmosphere. They were inhibited by adding a small amount of ethyl vinyl ether and the solutions were poured into an excess of methanol. The copolymers were purified by solubilization in chloroform containing a few drops of 1 N HCl and precipitation into methanol. The obtained copolymers were dried in a vacuum oven at 40˚C to constant weight.

0.5 g of 4 was added to 60 mL of solvent (dichloromethane-p-dioxane, 1:1) in a Schlenk tube. The catalyst (5 wt%) was previously introduced into a Parr shaker reactor. The solution was degassed and charged into the reactor under N₂. Then hydrogen was added. A 99% of hydrogenation, determined by ¹H NMR, for 5 was

Scheme 2. Synthesis of polynorbornene based copolymers via ROMP.

achieved using a Wilkinson’s catalyst, ClRh(PPh₃)₃, at room temperature and 115 bar (Scheme 3). The obtained polymer 5 was soluble in chloroform and dichloromethane. T_g1 = 143˚C; T_g2 = 198˚C; T_d = 460˚C; ¹H NMR (300 MHz, CDCl₃): d (ppm) = 7.48 - 7.23 (5H, m), 3.03 - 2.93 (2H, m), 2.17, 1.89, 1.60, 1.23; ¹³ C NMR (75 MHZ, CDCl₃): d (ppm) = 177.9 (C=O), 175.6 (C=O), 144.7-139.1 (C-F), 131.8, 128.9, 128.3, 126.4, 107.4 (C-N), 51.9, 44.0, 42.1, 33.7; ¹⁹F NMR (300 MHz, CDCl₃, ref. TFA [−77ppm]): d (ppm) = −142.2, −143.1, −150.2, −150.3, −159.8, −160.2; FT-IR (thin film, cm⁻¹): 2923 (C-H asym str), 2846 (C-H sym str), 1779 (C = O), 1706 (C = O), 1517, 1456 (C-N), 1359, 1299, (C-F), 1168, 1036, 988.

Hydrogenated poly(N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide-co-N-phenyl-exo-endo-norbornene-

5,6-dicarboximide) (5) ( 1.0 g , 1.74 mmol), sodium 4-hydroxybenzenesulfonate dihydrate ( 0.61 g , 2.62 mmol) and potassium carbonate ( 0.44 g , 3.18 mmol) were mixed in a round flask equipped with a Dean-Stark trap and stirred in 22 mL of solvent (N,N-dimethylacetamide-toluene, 10:1) at 120˚C for 5 h (Scheme 3). Progressive precipitation overtime was observed. The product was then filtered off, washed several times with distilled water and dried in a vacuum oven at 40˚C overnight. The resulting polymer 6, a pale-brown powder, was soluble in DMF and DMSO. Yield: 96%; T_g1 = 198˚C; T_g2 = 227˚C; T_d1 = 272˚C (sulfonic group loss); T_d2 = 458˚C (main chain decomposition); ¹H NMR (300 MHz, DMF-d₇): d (ppm) = 7.81 (2H, m), 7.53 - 7.34 (5H, m), 7.27 (2H, m), 3.65 (2H, s), 3.09, 2.24, 1.90, 1.65, 1.28; ¹³ C NMR (75 MHZ, DMSO-d₆): d (ppm) = 178.2 (C=O), 177.9 (C = O), 127.9 (C-O), 114.9, 107.5 (C-N), 51.6; ¹⁹ F NMR (300 MHz, DMF-d₇, ref. TFA [−77 ppm]): d (ppm) = −141.9, −142.9, −150.0, −153.1, −160.4; FT-IR (thin film, cm⁻¹): 3420, 2923 (C-H asym str), 2854 (C-H sym str), 1703 (C=O), 1698 (C=O), 1682, 1505, 1492, 1359, 1291 (C-F), 1165 (-SO₃H, asym str), 1124, 1033 (-SO₃H, sym str), 1008, 987, 742, 689, 608.