PDF《Technologies (COMSET),》

Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry

2006 S1 Facile Preparation of Fluorovinylene Aryl Ether Telechelic Polymers with Dual Functionality for Thermal Chain Extension and Tandem Crosslinking Scott T.

Iacono, Stephen M. Budy, Dirk Ewald, and Dennis W. Smith, Jr.* Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, SC

29634 Supplementary Information General Information. Chemicals and solvents were purchased through Aldrich or Alfa Aesar and used without purification unless otherwise stated. Bis(trifluorovinyloxy) aryl ether compounds (1), specifically 4,4'

-bis(4-trifluorovinyloxy)biphenyl (X = ?), 2,2-bis(4- trifluorovinyloxyphenyl)-1,1,1,3,3,3-hexafluoropropane (X = C(CF3)2), and 2,2-bis(4- trifluorovinyloxyphenyl)-1,1,1,3,3,3-propane (X = C(CH3)2), were donated and are commercially available from Tetramer Technologies, L.L.C., Pendelton, SC (www.tetramertechnologies.com) and distributed through Oakwood Chemicals, Inc., Columbia, SC (www.oakwoodchemical.com). All reactions were carried out under nitrogen (ultra high purity grade). Flasks and syringes were flamed-dried under vacuum and allowed to cool in dry box or desiccator prior to use.

1 H,

13 C (proton decoupled), and

19 F (proton decoupled) NMR data were obtained on a JOEL Eclipse+

300 and chemical shifts were reported in part per million (δ ppm).S1

1 H NMR was internally referenced to tetramethylsilane (δ 0.0),

13 C NMR chemical shifts were reported relative to the center peak of the multiplet for CDCl3 (δ 77.0 (t)), and

19 F NMR was referenced to CFCl3. Coupling constants for all spectra were reported in Hertz (Hz). Attenuated total reflectance Fourier transform infrared (ATRCFTIR) of neat samples and Fourier transform infrared (FTIR) analysis of samples prepared on KBr plates were performed on a ThermoNicolet Magna IR

550 FTIR Spectrophotometer. Gel permeation chromatography (GPC) data were collected in CHCl3 using polystyrene as a standard (Polymer Labs Easical PS-2) using a Waters

2690 Alliance System with refractive index detection at

35 °C. GPC samples were eluted in series through Polymer Labs PLGel

5 mm Mixed-D and Mixed-E columns. Differential scanning calorimetry (DSC) analysis and thermal gravimetric analysis (TGA) were performed on a TA Q1000 instrument and Mettler-Toledo

851 instrument, respectively. Glass transitions temperatures (Tg) of polymers were obtained from the second heating cycle using DSC analysis. Data collected with gas chromatography coupled with a mass spectrometer (GSCMS) were performed using a HP 5970. Melting points (mp) were measured using either DSC or a Mel-Temp melting point apparatus and are uncorrected. Yields are calculated from overall isolated mass. Preparation of Polymer 3. 2,2-Bis(4-hydroxyphenyl)hexafluoropropane (336 mg, 1.00 mmol) dissolved in anhydrous DMF (2 mL) was added drop wise to a stirred suspension of NaH (52.8 mg, 2.20 mmol) in DMF (2 mL) at room temperature for

1 h. 4,4'

-bis(4- trifluorovinyloxy)biphenyl (346 mg, 1.00 mmol) in DMF (2 ml) was transferred into the solution via syringe in a single portion. The solution was then heated to

80 °C for

24 h. The reaction was monitored the first few hours to see if solution gelled or solidified;

at this time additional DMF was added to maintain a constant stirring rate. The solution contents were then precipitated in H2O, filtered under vacuum, washed repeatedly with H2O, MeOH, and hexanes. The solid was dried in a vacuum oven at

60 °C for

24 h to afford the title compound as a pale yellow solid (550 Supplementary Material (ESI) for Chemical Communications This journal is ? The Royal Society of Chemistry

2006 S2 mg, 81%). ATRCFTIR (neat) ν

1607 (w),

1495 (m),

1172 (vs),

1114 (s),

829 (m) cm?1 ;

1 H NMR (CDCl3,

300 MHz) δ 7.80C6.80 (m), 6.20?6.70 (m);

19 F NMR (CDCl3,

283 MHz) δ C63.8 (s, C(CF3)2), C85.6 (s, CHFCF2), 120.8 (d, J = 32.8 Hz, cis-CF=CF), C122.2 (d, J = 49.3 Hz, cis- CF=CF), C126.6 (d, J = 111.8 Hz, trans-CF=CF), C128.6 (d, J = 111.7, trans-CF=CF), C138.5 (d, J = 59.2 Hz, CHFCF2). GPC in CHCl3 relative to polystyrene gave a monomodal distribution of Mn =

12 100 (Mw/Mn = 2.0). DSC analysis of second heating at

10 °C/min to

200 °C gave Tg =

88 °C and TGA (10 °C/min) gave Td (onset) =

324 and

554 °C in nitrogen and

551 °C in air. Preparation of Polymer 4a. 2,2-Bis(4-hydroxyphenyl)propane (500 mg, 2.20 mmol) was used for the addition to 4,4'

-bis(4-trifluorovinyloxy)biphenyl (871 mg, 2.20 mmol) using the procedure outlined for the preparation of

3 to obtain the title compound as a white solid (1.20 g, 88%). ATRCFTIR (neat) ν

2967 (w),

1604 (w),

1494 (vs),

1260 (vs),

1169 (vs),

1116 (vs),

824 (m) cm?1 ;

1 H NMR (DMSO-d6,

300 MHz) δ 7.70C7.7.56 (m), 6.85?6.65 (m), 3.15 (d, J = 5.64 Hz);

19 F NMR (DMSO-d6,

283 MHz) δ C84.5 (d, Jab = 150.0, CFHCF2), C85.4 (d, J = 150.0, CFHCF2) C121.4 (d, J = 39.5 Hz, cis-CF=CF), C122.0 (d, J = 39.4 Hz, cis-CF=CF), C128.2 (d, J = 108.5 Hz, trans-CF=CF), C128.7 (d, J = 108.5 Hz, trans-CF=CF), C141.1 (d, J = 55.9 Hz, CHFCF2). GPC in CHCl3 relative to polystyrene gave a monomodal distribution of Mn =

23 409 (Mw/Mn = 1.3). As a comparison using

19 F NMR, molecular weight relative to α,α,α- trifluorotoluene as an internal standard gave a calculated Mn =

15 000. DSC analysis of second heating at

10 °C/min to

200 °C gave Tg =

95 °C and TGA (10 °C/min) gave Td (onset) =

319 and

524 °C in nitrogen and

561 °C in air. Preparation of Polymer 4b. 2,2-Bis(4-hydroxyphenyl)propane (500 mg, 2.20 mmol), 4,4'

- bis(4-trifluorovinyloxy)biphenyl (871 mg, 2.20 mmol), and Cs2CO3 (358 mg, 1.10 mmol) in a minimal amount of DMF to initiate stirring was heated to

80 °C for

24 h. The reaction was monitored the first few hours to see if solution gelled or solidified;

at this time additional DMF was added to maintain a constant stirring rate. The solution contents were then precipitated in H2O, filtered under vacuum, washed repeatedly with H2O, MeOH, and hexanes. The solid was dried in a vacuum oven at

60 °C for

24 h to afford the title compound as a yellow solid (1.10 mg, 80%). ATRCFTIR (neat) ν

2969 (w),

1604 (w),

1495 (vs),

1269 (m),

1172 (vs),

1095 (vs),

823 (vs) cm?1 ;

1 H NMR (CDCl3,

300 MHz) δ 7.55?7.45 (m), 7.25C7.7.16 (m), 6.03?5.82 (m), 1.68 (s);

19 F NMR (CDCl3,

283 MHz) δ C85.4 (d, Jab = 151.0 CFHCF2), ?86.2 (d, J = 151.0 CFHCF2), C121.3 (d, J = 42.7 Hz, cis-CF=CF), C122.0 (d, J = 42.7 Hz, cis-CF=CF), C127.5 (d, J = 111.8 Hz, trans-CF=CF), C128.2 (d, J = 111.5 Hz, trans-CF=CF), C138.6 (d, J = 49.3 Hz, CHFCF2). GPC in CHCl3 relative to polystyrene gave a monomodal distribution of Mn =

11 771 (Mw/Mn = 1.7). DSC analysis of second heating at

10 °C/min to

200 °C gave Tg =

34 °C and TGA (10 °C/min) gave Td (onset) =

336 and

513 °C in nitrogen and

632 °C in air. Preparation of Polymer 5. 2,2-Bis(4-hydroxyphenyl)hexafluoropropane (500 mg, 1.48 mmol) was used for the addition to 2,2-bis(4-trifluorovinyloxyphenyl)-1,1,1,3,3,3-hexafluoropropane (893 mg, 1.48 mmol) using the procedure outlined for the preparation of

3 to obtain the title compound as a pale yellow solid (450 mg, 32%). ATRCFTIR (neat) ν

1610 (w),

1511 (m),

1173 (vs),

1120 (m),

829 (vs)........