Facile synthesis of a high molecular weight amphiphilic aramid–ROMP block copolymer

Supporting Information for

Facile synthesis of a high molecular weight amphiphilic

aramid-ROMP block copolymer.

Michael Badoux, Susanne Drechsler, Andreas F.M. Kilbinger*

University of Fribourg, Chemistry Department, Chemin du Musée 9, CH-1700 Fribourg, Switzerland

 

Contents  

 

Scheme for the synthesis of the poly(perfluorophenyl 4-((2,4-dimethoxybenzyl) amino) benzoate)

block (PAram block).  ...  2

 

Synthesis of the

poly(2-(3-(dimethylamino)propyl)-3a,4,7,7a-tetrahydro-1H-4,7-methano-isoindole-1,3(2H)-dione) amine end functionalized block (PDMAPNI block).  ...  2

 

NMR spectra of monomer 2 and the Param polymer.  ...  3

 

NMR spectra of the monomer 3 and the PDMAPNI polymer.  ...  5

 

NMR spectra of the block copolymer PDMAPNI-b-Param after coupling and post-modifications.  ....  6

 

GPC elugrams of the PDMAPNI and PAram polymer blocks after and before coupling.  ...  10

 

Transmission electron microscopy pictures of the block copolymers at the different stages:  ...  12

 

Scheme for the synthesis of the poly(perfluorophenyl 4-((2,4-dimethoxybenzyl) amino)

benzoate) block (PAram block).

Synthesis of the

poly(2-(3-(dimethylamino)propyl)-3a,4,7,7a-tetrahydro-1H-4,7-methano-isoindole-1,3(2H)-dione) amine end functionalized block (PDMAPNI block).

OH O H2N O O O AcOH, THF NaBH(OAc)3 r.t., 12 h. OH O HN O O HO DCC, DMAP DCM, r.t., 12 h. O O HN F F F F F N O O O O O F F F F F n

PAram

BuLi, TMP Phenyl benzoate THF, -60°C overnight F F F F F

1

2

O O

NMR spectra of monomer 2 and the Param polymer.

BMP5-­461  -­  H.ESP 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 Chemical  Shift  (ppm) 6.37 2.13 0.89 2.09 2.07 1.03 2.00 Ethyl  acetate CDCl3 3 .8 2 3 .8 6 4 .3 6 6 .4 5 6 .4 7 6 .5 1 6 .5 1 6 .6 5 6 .6 7 7 .1 7 7 .1 9 7 .9 8 8 .0 0 1_{H NMR (CDCl} 3, 400MHz) spectrum of monomer 2. BMP5-­461  -­  F  RECRYST.ESP -­120 -­125 -­130 -­135 -­140 -­145 -­150 -­155 -­160 -­165 -­170 -­175 -­180 -­185 -­190 Chemical  Shift  (ppm) 2.24 1.01 2.00 -­1 63 .0 8 -­1 59 .2 0 -­1 52 .7 4 -­1 52 .6 9 19_{F NMR (CDCl} 3, 376MHz) spectrum of monomer 2.

BMPP5-­08E  -­  H  DMF.ESP 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 Chemical  Shift  (ppm) 2.86 3.00 1.73 1.99 1.84 1.95 1.00 Water 3.4 7 3.5 6 3.7 1 5.0 1 6.4 4 6.4 6 6.4 8 6.8 7 6.8 9 7.0 7 7.0 9 7.2 3 1_{H NMR (DMF-d}

7, 400MHz) spectrum of the PAram block.

BMPP5-­08E  -­  F.ESP 20 0 -­20 -­40 -­60 -­80 -­100 -­120 -­140 -­160 -­180 -­200 -­220 Chemical  Shift  (ppm) -­1 63 .0 6 -­1 59 .1 9 -­1 52 .6 8 19_{F NMR (DMF-d}

NMR spectra of the monomer 3 and the PDMAPNI polymer.

SD  MONOMER  -­  H  CDCL3.ESP 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 0.01 1.13 0.02 1.09 2.05 6.00 1.99 1.95 2.40 2.12 2.04 1 .1 9 1 .2 2 1 .4 8 1 .5 0 1 .7 0 1 .7 2 2 .1 9 2 .2 8 2 .3 0 2 .6 5 2 .6 5 3 .2 4 3 .2 5 3 .2 5 3 .5 0 3 .5 2 6 .2 6 6 .2 6 6 .2 7 1_{H NMR (CDCl}

3, 400MHz) spectrum of the monomer 3.

2017-­03-­14_PolSD001_DMSO_001001r 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 2.00 0.93 3.23 1.51 1.09 1.80 1.23 DMSO Water 1.5 7 1.5 9 2.0 0 2.1 1 2.2 0 2.6 4 2.6 7 3.0 2 3.0 3 5.3 1 5.4 8 5.6 6 5.6 8 1_{H NMR (DMSO-d}

2017-­03-­10_PolSD002_DMSO_001001r 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 2.54 2.00 2.38 2.09 8.27 5.49 2.37 DMSO Water 1.2 4 1.5 3 1.8 8 1.9 9 2.0 1 2.7 0 3.0 1 3.0 7 5.3 2 5.5 0 5.7 0 1_{H NMR (DMSO-d}

6, 400MHz) spectrum of PDMAPNI (with a free amine at the chain end). The shift of the

methyl amine peak from 2.11 to 2.7 ppm is probably due to the protonation of the dimethylamine by HCl.

NMR spectra of the block copolymer PDMAPNI-b-Param after coupling and

post-modifications.

BMPSD_001001r 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 4.15 1.78 2.00 1.69 1.94 1.18 1.1 1 1.3 0 1.6 2 1.6 7 1.7 8 2.1 3 2.3 3 2.4 9 2.7 9 3.1 6 3.7 1 5.0 1 5.7 9 5.8 3 6.4 4 6.4 6 6.4 8 6.8 7 6.8 9 7.0 7 7.0 9 7.2 3 7.2 5 8.0 3 1_{H NMR (DMF-d}

7, 400MHz) spectrum of the block copolymer (PAram-b-PDMAPNI) after recycling GPC

BMPSD_001001r 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 1.00 1.31 1.13 2.03 1.26 5.57 1.86 2.24 1.83 1 .1 1 1 .3 0 1 .6 2 1 .6 7 1 .7 8 2 .1 3 2 .3 3 2 .4 9 2 .7 9 3 .1 6 3 .7 1 5 .0 1 5 .7 9 5 .8 3 6 .4 4 6 .4 6 6 .4 8 6 .8 7 6 .8 9 7 .0 7 7 .0 9 7 .2 3 7 .2 5 8 .0 3 1_{H NMR (DMF-d}

7, 400MHz) spectrum of the block copolymer (PAram-b-PDMAPNI) after recycling GPC

(integration of the PDMAPNI block).

BMPSD_004001r

20 0 -­20 -­40 -­60 -­80 -­100 -­120 -­140 -­160 -­180 -­200 -­220 Chemical  Shift  (ppm)

19_{F NMR (DMF-d}

7, 376MHz) spectrum of the block copolymer (PAram-b-PDMAPNI). Due to amide

BMPSD.006.001.2rr.esp 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 F2  Chemical  Shift  (ppm) -­9.9 -­9.8 -­9.7 -­9.6 -­9.5 -­9.4 -­9.3 -­9.2 -­9.1 -­9.0 -­8.9 F 1  Ch em ica l  S hift   (p pm ) 1_{H NMR (DMF-d}

7, 400MHz) Diffusion Ordered Spectroscopy (DOSY) spectrum of the block copolymer

(PAram-b-PDMAPNI). BMPSD  +  MEI  -­  H.ESP 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 0.67 0.81 2.14 1.33 1.02 1.80 5.93 4.10 4.52 1.33 1.59 2.00 1.55 1.74 1.04 1 .2 9 1 .4 7 1 .8 3 2 .3 0 2 .3 9 3 .0 3 3 .2 4 3 .5 6 3 .7 4 3 .7 5 3 .9 0 3 .9 1 5 .1 9 5 .7 8 6 .0 1 6 .6 6 7 .0 5 7 .2 5 7 .4 1 1_{H NMR (DMF-d}

7, 400MHz) spectrum of the block copolymer after addition of methyl iodide

BMPSD.008.001.2rr.esp 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 F2  Chemical  Shift  (ppm) -­10.0 -­9.9 -­9.8 -­9.7 -­9.6 -­9.5 -­9.4 -­9.3 -­9.2 -­9.1 -­9.0 -­8.9 -­8.8 -­8.7 -­8.6 F 1  Che m ica l  S hift  ( pp m ) 1_{H NMR (DMF-d}

7, 400MHz) Diffusion Ordered Spectroscopy (DOSY) spectrum of the block copolymer after

addition of methyl iodide (PAram-b-PTMAPNI).

BMPSD_013001r 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 Chemical  Shift  (ppm) 1.00 3.00 1.69 1.84 11.31 2.14 1.60 2.35 1.8 1 2.2 8 2.9 5 3.0 9 3.3 4 3.6 0 5.7 4 5.9 5 1_{H NMR (D}

2O:DMF-d7,1:1, v:v 400MHz) spectrum of the block copolymer (PAram-b-PDMAPNI) after

addition of D2O (50%) to the block copolymer in DMF-d7 (50%) (spectrum measured with a proton diffusion

GPC elugrams of the PDMAPNI and PAram polymer blocks after and before coupling.

Evolution of the gel permeation chromatography elugrams (in DMF, RI signal) showing the reaction between the two blocks after 24, 48 and 120 hours.

Comparison of the gel permeation chromatography elugrams (in DMF, RI signal) of the two blocks before coupling. (PAram block: Mn 19'000 / Mw 33'000 / PDI 1.74, PDMAPNI block: Mn 24'400 / Mw 45'900 / PDI 1.88). 10 12 14 16 18 20 22 minutes After  24  hours After  48  hours After  120  hours 0 5 10 15 20 25 minutes PAram  block PDMAPNI  block

Gel permeation chromatography of the pure block copolymer (PAram-b-PDMAPNI) in chloroform. (RI signal, Mn 27'000 / Mw 43'500 / PDI 1.61).

0 5 10 15 20 25 30

Transmission electron microscopy pictures of the block copolymers at the different stages:

 

Transmission electron microscopy micrographs of the block copolymer PAram-b-PDMAPNI. (drop cast from DMF, ca. 30 mg/mL).

Transmission electron microscopy micrographs of the block copolymer PAram-b-PDMAPNI after quaternization with methyl iodide (PAram-b-PTMAPNI, Scheme 3 ST1). (drop cast from DMF, ca. 30 mg/mL).

Transmission electron microscopy micrographs of the quaternized block copolymer PAram-b-PTMAPNI (Scheme 3 ST2) after addition of water until reaching a ratio of 1:1 DMF/water. Different type of aggregates are visible. (Concentration around 10 mg/mL, drop cast from DMF/water).

Transmission electron microscopy micrographs of the quaternized block copolymer PAram-b-PTMAPNI (Scheme 3 ST3) in a 1:1 DMF/water mixture after addition of trifluoroacetic acid. Cleavage of the N-benzyl protecting groups on the PAram blocks induces strong aggregation and formation of fibers. (Concentration around 10 mg/mL, drop cast from DMF/water).