Synthesis and properties of poly(norbornene)s with lateral aramid groups
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(311) Figure S 1 H NMR spectra (400 MHz, CHLOROFORM-d) for determination of DMBdeprotection. 1. 15.
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(316) . .
(317) . Figure S 2 Correlation functions and corresponding hydrodynamic radius calculated from DLS on polymer solutions of 0.5 mg mL in THF. Note: Due to strong aggregation polROD-P35 and polROD-P50 were not possible to measure by means of DLS due to solubility problems. -1. $ ! !! /&*$P)(+# !&(10"/1/,"*/&+*/<! 0 3"." +((" 0"! 0 +*/0 *0.++)0"),". 01."EPOKF+* +))". & ($+*&+)"0".&*/0.1)"*0EQ," 0.+)"0".< */0.1)"*0/ <3&06".( *!F?%" ,.&) .5 " )3 /#+.)"! 5 (&*" .(5,+( .&6"! *! +((&) 0"!( /". " )E+ +(0NSBNO!&+!" ,1),"!/+(&!/0 0"( /".<:\TTN*)<?\SNN)F< *!0%"/ 00"."!(&$%03 / +((" 0"! 5 /&*$("B)+!"+,0& (#& "./"-1&,,"!3&0%&*0"$. 0"! +((&) 0&+*+,0& /?%"&* +)&*$( /". " ) , //"!0%.+1$% ( *B%+),/+*,+( .&6".3&0% *"40&* 0&+*. 0&++#ONBT< *! *+0%". ( *B. 16.
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igure S 3 GPC data (solvent THF, polystyrene standards) of aged (2 month) polEtHexROD.. 17.
(319) Figure S 4 Determination of practical rod content by H NMR spectra (400 MHz, CHLOROFORM-d) comparison of polDMBrod. 1. 18.
(320) Figure S 5 Determination of practical rod content by CHLOROFORM-d) comparison of polEtHexROD. 1H. NMR spectra (400 MHz,. 19.
(321)
(322). . . . . . . . . . . . . . . . Figure S 6 DSC curvatures indicating first heating, cooling and second heating cycles for polEHNI, polDMBrod, polROD and polEHNI samples between -80 and 300°C at heating rate of 10 K min . -1. 20.
(323) Figure S 7 DSC curvatures obtained from polROD and polEHNI samples annealed 15°C above their respective T for 1 h and subsequent slow cooling to room temperature. Second heating cycle reported. g. b . 50. . 30. c. . 20. . d 10. 2.0. . . Strain ε [%]. 3.0. . 1.0.
(324). 0 0.0. .
(325) . Stress σ [MPa]. 40. . polEHNI polDMBrod-P10 polROD-P10 polEtHexROD-P10. . Figure S 8 (a) Tensile stress-strain curves measured at 25°C. One representative curve per composition is shown and the curves were cut at maximum stress for clarity. Also shown are averages of (b) maximum stress, (c) elongation at maximum stress, and (d) Young’s modulus determined from the tensile tests. Experiments were conducted at least in triplets.. 21.
(326) ?. Figure S 9 Tensile stress-strain-curvature derived from DMA experiments at 25°C.. Storage Modulus E' [MPa]. 1000. polEHNI polDMBrod-P10 polROD-P10 polEtHex-P10. 100. 10. 1 0. 50. 100. 150. 200. Temperature [°C] Figure S 10 Temperature dependence of storage modulus E’ obtained via DMA experiments on 0.12 ± 0.01 mm hot-pressed films of all polymer samples. 22.
(327) . .
(328) .
(329).
(330) .
(331).
(332) .
(333) .
(334) . Figure S 11 Photographs of transmission and cross-polarized light microscopy of polymers obtained from precipitation. (Scale bar all 100 μm, except polEtHexROD-P25 is 50 µm and polROD-P25 is 200 µm.). 23.
(335) " . " !. . . !. .
(336) . . . .
(337) . . Figure S 12 Photographs of transmission and cross-polarized light microscopy of polymers obtained from precipitation. Pictures taken below and above 250°C. Scale bar all: 100 μm (except polROD-P25 is 200 μm).. 24.
(338) +
(339) "! . +
(340) $!%%"! $ *. . $!%%"! $ *. . "! &) . . . . +
(341) !$ %'%#' &% !(!! "! "! . . Figure S 13 Photographs of transmission and cross-polarized light microscopy of polymers obtained from precipitation. Pictures taken below and above 250°C. Scale bar all 100 µm, except polEtHexROD-P25 is 50 µm. 25.
(342)
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