supporting information dicyclopentadiene derivatives cross … · 2016. 4. 14. · 44 dsc plot for...

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Supporting InformationCross-linked ROMP polymers based on odourless dicyclopentadiene derivatives

Sukdeb Saha, Yakov Ginzburg, Illya Rozenberg, Olga Iliashevsky, Amos Ben-Asuly and N. Gabriel Lemcoff*Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel

Serial No.

Contents Page No.

1 Experimental 32 1H NMR of DCPD-OH (2) in CDCl3 63 13C NMR of DCPD-OH (2) in CDCl3 74 HMQC spectra of DCPD-OH (2) in CDCl3 85 1H NMR of DCPD-OAc (3a) in CDCl3 96 13C NMR of DCPD-OAc (3a) in CDCl3 107 COSY NMR of DCPD-OAc (3a) in CDCl3 118 HMQC spectra of DCPD-OAc (3a) in CDCl3 129 HRMS spectra of DCPD-OAc (3a) 1310 1H NMR spectra of DCPD-OBz (3b) in CDCl3 1411 13C NMR spectra of DCPD-OBz (3b) in CDCl3 1512 COSY spectra of DCPD-OBz (3b) in CDCl3 1613 HMQC spectra of DCPD-OBz (3b) in CDCl3 1714 HRMS spectra of DCPD-OBz (3b) 1815 1H NMR spectra of DCPD-OMe (4a) in CDCl3 1916 13C NMR spectra of DCPD-OMe (4a) in CDCl3 2017 COSY NMR spectra of DCPD-OMe (4a) in CDCl3 2118 HMQC NMR spectra of DCPD-OMe (4a) in CDCl3 2219 HRMS spectra of DCPD-OMe (4a) 2320 1H NMR spectra of DCPD-OPr (4b) in CDCl3 2421 13C NMR spectra of DCPD-OPr (4b) in CDCl3 2522 COSY NMR spectra of DCPD-OPr (4b) in CDCl3 2623 HMQC NMR spectra of DCPD-OPr (4b) in CDCl3 2724 HRMS spectra of DCPD-OPr (4b) 2825 1H NMR spectra of DCPD-OOc (4c) in CDCl3 2926 13C NMR spectra of DCPD-OOc (4c) in CDCl3 3027 COSY NMR spectra of DCPD-OOc (4c) in CDCl3 3128 HMQC spectra of DCPD-OOc (4c) in CDCl3 3229 HRMS spectra of DCPD-OOc (4c) 3330 TGA plot of DCPD monomer (1) 34

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2016

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31 TGA plot of DCPD-OH monomer (2) 3532 TGA plot of DCPD-OAc (3a) monomer 3633 TGA plot of DCPD-OBz (3b) monomer 3734 TGA plot of DCPD-OMe (4a) monomer 3835 TGA plot of DCPD-OPr (4b) monomer 3936 TGA plot of DCPD-OOc (4c) monomer 4037 TGA plot of pDCPD after 2h of curing 4138 TGA plot of pDCPD-OH after 2h of curing 4239 TGA plot of pDCPD-OAc after 2h of curing 4340 TGA plot of pDCPD-OBz after 2h of curing 4441 TGA plot of pDCPD-OMe after 2h of curing 4542 TGA plot of pDCPD-OPr after 2h of curing 4643 TGA plot of pDCPD-OOc after 2h of curing 4744 DSC plot for pDCPD 4845 DSC plots for dicyclopentadiene derivatives polymers 4946 DMA plot for pDCPD 5047 DMA plot for pDCPD-OH 5148 DMA plot for pDCPD-OAc 5249 DMA plot for pDCPD-OBz 5350 DMA plot for pDCPD-OMe 5451 DMA plot for pDCPD-OPr 5552 DMA plot for pDCPD-OOct 5653 Image for wetting of pDPCD-OH, co-(pDCPD-OH-pDCPD-OPr) and

pDCPD-OPr56

54 FTIR for DCPD-OH (2) 5755 FTIR for DCPD-OAc (3a) 5856 FTIR for DCPD-OPr (4b) 5957 Procedure of thin films preparation and FTIR for pDCPD-OH thin film 6058 FTIR for pDCPD-OAc thin film 6159 FTIR for pDCPD-OPr thin film 6260 FTIR for linear pDCPD-OAc thin film 6361 FTIR for linear pDCPD-OPr thin film 64

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General Experimental: All the starting materials, solvents and reagents were obtained commercially and used without any further purification unless described otherwise. DMF and dichloromethane were dried by passing through a solvents drying machine. HR-MS data were obtained using a thermoscientific LTQU XL Orbitrap HR-MS equipped with APCI (atmospheric pressure chemical ionization). 1H and 13C NMR spectra were recorded either with Bruker 400 MHz or 500 MHz FT NMR (model Avance-DPX 400 or DPX 500). The TGA analysis was performed using a Mettler-Toledo instrument model TGA/SDTA851. 5-7 mg sample were heated in a standard 70 µL TGA alumina crucible from room temperature to 600°C, with a heating rate of 10°C/min in nitrogen atmosphere 50ml/min. The results were analysed by STARe software 12.00. The cross-linked thermoset polymers were also subjected to the differential scanning calorimetric analysis (DSC) with a METTLER-TOLEDO DSC 823 and results were evaluated with the STARe software. Each sample was subjected to a 2-3 heating cooling cycles. Each cycle contained a heating segment followed by a cooling segment at a heating rate of 5°C/min. The viscoelastic properties of the pDCPD-OR were evaluated from 25°C to lowest storage modulus (E) temperature with the heating rate of 2°C/min using dynamic mechanical analysis (DMA) (METTLER TOLEDO DMA 1 STARe system) at different frequencies e.g. 0.1 Hz, 1 Hz and 10 Hz while experimental results were evaluated using the STARe software version 14.00. However, for very soft material like pDCPD-OOc, the measurement was performed with in the temperature range -100°C to 10°C until the E reached a minimum value at the same frequencies. The values of the storage modulus (E), loss modulus (E) and loss tangent (tan = E/E) for multiple frequencies were measured as a function of temperature. FTIR for the thin films was measured by using a Jasco FT/IR-460 Plus Fourier transform infrared spectrometer.

Synthesis and characterization of the monomers:Synthesis of endo-DCPD-OH (2): endo-dicyclopentadiene (1) (40.0 g, 0.303 mol) was dissolved in 120 ml of dioxane/H2O (9:1, v/v) solution. Selenium dioxide (40.08 g, 0.361 mol) was added in one portion; the solution was refluxed for 3 hours and cooled to room temperature. The solvent was removed under reduced pressure and the viscous brown oil was dissolved in 200 ml of diethyl ether, dried on magnesium sulfate, filtered and the solvent again evaporated. The crude brown oil was distilled at 1.5 mbar, the fraction at 74-76°C was collected to afford approximately 30 g as a pale yellow oil which crystallized at 4°C to a pale yellow solid, m.p. 30-35°C (isolated yield 67%). Boiling point: 216 -217°C.1H NMR (400 MHz, CDCl3, ppm): δ 5.91 (dd, J = 5.7, 3.0 Hz, 1H), 5.82 (dd, J = 5.7, 3.0 Hz, 1H), 5.78 – 5.71 (m, 1H), 5.61 – 5.55 (m, 1H), 4.04 (m, 1H), 3.35 (m, 1H), 3.03 (m, 1H), 2.77 (m, 1H), 2.51 (m, 1H), 1.95 (s, 1H), 1.54 (m, 1H), 1.37 (m, 1H).13C NMR (100 MHz, CDCl3, ppm): δ 137.76, 135.41, 134.63, 132.38, 78.92, 54.64, 53.37, 51.23, 44.77 and 44.62.

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General procedure for esterification of 2 (3a-b): A three necked round bottom flask was charged with 2 (1 gm, 6.75 mmol) and was subjected to vacuum and then nitrogen consecutively three times. Then, dry DCM (50 ml) and Et3N (1.5 ml) were added to it and the solution was stirred at 0°C for 10 min. After that, the corresponding acid chloride (10.13 mmol) was added through syringe in dropwise fashion. It was then kept for 12h stirring at room temperature. After that, it was washed with water. The organic layer was separated and dried over MgSO4. It was finally concentrated and subjected to flash column chromatography for purification. The expected product was eluted with ethyl acetate/ petroleum ether (1: 19) on neutral alumina stationary phase.

3a: Colorless liquid, isolated yield: 85%, boiling point: 224-226°C. HRMS: calculated for C12H14O2 as m/z (M+Na+) 213.0891; found 213.0888.1H NMR (500 MHz, CDCl3, ppm) (3a): 6.03 (dd, J = 5.5, 3.0 Hz, 1H), 5.88 (bd, J = 5.5 Hz, 1H), 5.86 (dd, J = 5.5, 3.0 Hz, 1H), 5.57 (bd, J = 5.5 Hz, 1H), 4.96 (bs, 1H), 3.38-3.37 (m, 1H), 3.10 (bs, 1H), 2.82 (bs, 1H), 2.61 – 2.59 (m, 1H), 2.02 (s, 3H), 1.58 (bd, J = 8.2 Hz, 1H), 1.40 (bd, J = 8.2 Hz, 1H).13C NMR (125 MHz, CDCl3, ppm) (3a): 171.22, 140.15, 135.48, 132.68, 130.86, 82.23, 54.67, 51.47, 50.37, 44.94, 44.84 and 21.51.

3b: White solid (m. p. 700C), isolated yield: 82%. HRMS: calculated for C17H16O2 as m/z (M+Na+) 275.1048; found 275.1052. 1H NMR (500 MHz, CDCl3, ppm) (3b): 8.03 (bd, J = ~8 Hz, 2H), 7.54 (bt, J = 7.5 Hz, 1H), 7.42 (bt, J = 7.5 Hz, 2H), 6.11 (dd, J = 5.5, 3.0 Hz, 1H), 5.95 (bd, J = 5.7 Hz, 1H), 5.91 (dd, J = 5.5, 3.0 Hz, 1H), 5.70 (bd, J = 5.7 Hz, 1H), 5.21 – 5.20 (m, 1H), 3.46 – 3.43 (m, 1H), 3.19 (bs, 1H), 2.86 (bs, 1H), 2.78 – 2.75 (m, 1H), 1.62 (bd, J = 8.5 Hz, 1H), 1.44 (bd, J = 8.5 Hz, 1H).13C NMR (125 MHz, CDCl3, ppm) (3b): 166.83, 140.28, 135.57, 132.89, 132.83, 131.00, 130.82, 129.69, 128.41, 82.90, 77.41, 77.16, 76.91, 54.84, 51.57, 50.55, 45.00 and 44.93.

General procedure for etherification of 2 (4a-c):A three necked round bottom flask was charged with 2 (1 gm, 6.75 mmol) and NaH (405 mg, 10.13 mmol, 60%) and it was subjected to vacuum and then nitrogen consecutively three times. Then, dry DMF (20 ml) was added to it and was stirred at 0°C for 10 min, a purple coloured solution was observed. After that, 1-iodoalkane (10.13 mmol) was added through syringe in dropwise fashion, the purple colour disappeared and a pale white solution was observed. It was then kept for 12h stirring at room temperature. After that, it was diluted with ethyl acetate (60 ml) and washed with saturated aq. NH4Cl solution. The organic layer was then separated and dried over MgSO4. It was finally concentrated and subjected to flash column chromatography for purification. The expected product was eluted with ethyl acetate/ petroleum ether (1: 19) on silica gel stationary phase as a c liquid.

4a: Colorless liquid, isolated yield: 84%.boiling point: 214-217°C HRMS: calculated for C11H14O as m/z (M+Na+) 185.0942; found 185.9305.

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1H NMR (500 MHz, CDCl3, ppm)(4a): 5.95 (bdd, J = 5.7, 2.7 Hz, 1H), 5.86 (bdd, J = 5.5, 3.0 Hz, 1H), 5.82 (bd, J = 5 Hz, 1H), 5.65 (bd, J = 5.5 Hz, 1H), 3.71 (bs, 1H), 3.38 – 3.35 (m, 1H), 3.31 (s, 3H), 2.99 (bs, 1H), 2.79 (bs, 1H), 2.62 – 2.59 (m, 1H), 1.58 (bd, J = 8.2 Hz, 1H), 1.43 (bd, J = 8.2 Hz, 1H). 13C NMR (125 MHz, CDCl3, ppm) (4a): 138.66, 135.57, 132.50, 131.96, 88.02, 55.75, 54.84, 51.46, 49.71, 45.36, and 44.68.

4b: Colorless liquid, isolated yield: 91%. Boiling point: 216-218°C HRMS: calculated for C13H18O as m/z (M+Na+) 213.1255; found 213.1257.1H NMR (400 MHz, CDCl3, ppm)(4b): 5.96 (bdd, J = 5.8 Hz, 3 Hz, 1H), 5.86 (bdd, J = 5.8, 3.0 Hz, 1H), 5.80 (bd, J = 5.6 Hz, 1H), 5.65 – 5.63 (m, 1H), 3.78-3.76 (m, 1H), 3.47-3.31 (m, 3H), 2.99 (bs, 1H), 2.79 (bs, 1H), 2.63-2.59 (m, 1H), 1.63 – 1.56 (m, 3H), 1.42 (d, J = 8 Hz, 1H), 0.92 (t, 7.5 Hz, 3H).13C NMR (125 MHz, CDCl3, ppm) (4b): 138.24, 135.58, 132.54, 132.50, 86.61, 70.33, 54.85, 51.47, 50.18, 45.37, 44.67, 23.44 and 10.84.

4c: Colorless liquid, isolated yield: 59%. Boiling point: 220-222°C. HRMS: calculated for C18H28O as m/z (M+Na+) 283.2038; found 283.20215. 1H NMR (500 MHz, CDCl3, ppm) (4c): 5.95 (bdd, J = 5.5, 3 Hz, 1H), 5.86 (bdd, J = 5.5, 3.0 Hz, 1H), 5.80 (bd, J = 6 Hz, 1H), 5.63 (bd, J = 5.5 Hz, 1H), 3.76 (bs, 1H), 3.49 – 3.44 (m, 1H), 3.39 – 3.34 (m, 2H), 2.99 (bs, 1H), 2.78 (bs, 1H), 2.62 – 2.59 (m, 1H), 1.58 – 1.53 (m, 3H), 1.42 (bd, J = 8.1 Hz, 1H), 1.35 – 1.27 (m, 10H), 0.88 (t, J = 6.9 Hz, 3H).13C NMR (125 MHz, CDCl3, ppm) (4c): 138.24, 135.59, 132.56, 132.52, 86.64, 68.74, 54.86, 51.48, 50.19, 45.39, 44.69, 31.98, 30.30, 29.63, 29.41, 26.45, 22.81 and 14.24.

General procedure for polymerizations:1 mmol of monomer was introduced to a 4 ml glass vial and then 2nd generation Grubbs’ catalyst (2.0 x 10-4 mmol) dissolved in a small amount of dry CH2Cl2 (~50 l) was added. After mixing the solution very quickly, the solvent was removed by gentle blowing of argon and the remaining mixture was transferred into a rectangular shaped (2 cm x 1 cm x 1 mm) aluminum mold and placed in an oven of pre-set temperature at 700C for 30 min to produce the highly cross-linked solid polymer. For 3b, the monomer was melted first at 1000C in the oven and then a latent catalyst (cis-Ru-SPh or cis-Ru-SiPr) was added quickly to obtain the polymer.

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Figure 1: 1H NMR of DCPD-OH (2) in CDCl3.

OH

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Figure2: 13C NMR of DCPD-OH (2) in CDCl3.

OH

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Figure 3: HMQC spectra of DCPD-OH (2) in CDCl3.

OH

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Figure 4: 1H NMR of DCPD-OAc (3a) in CDCl3.

OCOCH3

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Figure 5: 13C NMR of DCPD-OAc (3a) in CDCl3.

OCOCH3

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Figure 6: COSY NMR of DCPD-OAc (3a) in CDCl3.

OCOCH3

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Figure 7: HMQC spectra of DCPD-OAc (3a) in CDCl3.

OCOCH3

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Figure 8: HRMS spectra of DCPD-OAc (3a).

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213.08860

403.18798

NL:2.76E8ZA-009_in_90%DCM+10%MeOH_102-1000#46 RT: 0.21 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:3.93E7za-009_blank_90%dcm+10%meoh_102-1000#41 RT: 0.19 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:8.73E5C 12 H14 O2 Na: C 12 H14 O2 Na 1pa Chrg 1


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Figure 9: 1H NMR spectra of DCPD-OBz (3b) in CDCl3.

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Figure 10: 13C NMR spectra of DCPD-OBz (3b) in CDCl3.

OCOPh

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O

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Figure 11: COSY spectra of DCPD-OBz (3b) in CDCl3.

OCOPh

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Figure 12: HMQC spectra of DCPD-OBz (3b) in CDCl3.

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Figure 13: HRMS spectra of DCPD-OBz (3b).

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275.10425

527.21928

NL:1.01E8ZA-008N_in_90%DCM+10%MeOH_102-1000#42 RT: 0.22 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:3.73E7za-008_blank_90%dcm+10%meoh_102-1000#38 RT: 0.20 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]



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Figure 14: 1H NMR spectra of DCPD-OMe (4a) in CDCl3.

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Figure 15: 13C NMR spectra of DCPD-OMe (4a) in CDCl3.

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Figure 16: COSY NMR spectra of DCPD-OMe (4a) in CDCl3.

1.62.02.42.83.23.64.04.44.85.25.66.06.4f2 (ppm)

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Figure 17: HMQC NMR spectra of DCPD-OMe (4a) in CDCl3.

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Figure 18: HRMS spectra of DCPD-OMe (4a).

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NL:2.08E7ZA-010 90%DCM+10%MeOH_102-1000#30 RT: 0.20 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:3.27E7za-010 blankdcm+meoh_102-1000#45 RT: 0.20 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:8.85E5C 11 H14 ONa: C 11 H14 O1 Na 1pa Chrg 1

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Figure 19: 1H NMR spectra of DCPD-OPr (4b) in CDCl3.

OCH2CH2CH3

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Figure 20: 13C NMR spectra of DCPD-OPr (4b) in CDCl3.

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Figure 21: COSY NMR spectra of DCPD-OPr (4b) in CDCl3.

OCH2CH2CH3

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Figure 22: HMQC NMR spectra of DCPD-OPr (4b) in CDCl3.

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Figure 23: HRMS spectra of DCPD-OPr (4b).

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NL:2.47E8GY-902 in90%DCM+10%MeOH_102-1000#46 RT: 0.25 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:1.20E8gy-902-blank 90%dcm+10%meoh_102-1000#53 RT: 0.25 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]


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Figure 24: 1H NMR spectra of DCPD-OOc (4c) in CDCl3.

O(CH2)7CH3

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Figure 25: 13C NMR spectra of DCPD-OOc (4c) in CDCl3.

O(CH2)7CH3

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Figure 26: COSY NMR spectra of DCPD-OOc (4c) in CDCl3.

O(CH2)7CH3

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Figure 27: HMQC NMR spectra of DCPD-OOc (4c) in CDCl3.

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Figure 28: HRMS spectra of DCPD-OOc (4c).

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600000

0

200000

400000

600000

800000

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

283.20215z=1

543.41577z=1

131.08498z=1

410.30075z=2

313.21301z=1

242.28371z=1

579.29150z=1

919.50000z=1

815.62128z=1

301.14023z=1

179.01651z=?

379.15427z=1

579.29163z=1

225.10912z=1

659.28644z=1

937.43823z=1

802.51984z=?

283.20324

543.41725

NL:1.18E9GY-900_in_90%DCM+10%MeOH_102-1000#25 RT: 0.17 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]

NL:7.75E7gy-900 blank90%dcm+10%meoh_102-1000#25 RT: 0.17 AV: 1 T: FTMS + c NSI Full ms [102.00-1000.00]



Blank

4c+Na+

2x 4c+Na+

4c

O(CH2)7CH3

34

TGA condition:

TGA was performed with a heating rate of 10°C/min up to 600°C in an isothermal way under N2 atmosphere with flow rate of 90 ml/min.

Figure 29: TGA of DCPD (1).

35

Figure 30: TGA of DCPC-OH (2).

36

Figure 31: TGA of DCPC-OAc (3a).

37

Figure 32: TGA of DCPC-OBz (3b).

38

Figure 33: TGA of DCPC-OMe (4a).

39

Figure 34: TGA of DCPC-OPr (4b).

40

Figure 35: TGA of DCPC-OOc (4c).

41

A summary of selected TGA values is given in the table below:

Polymer

5% weight loss

T(°C)

10% weight loss T(°C)

Main chain maximum decomposition rate T (°C)

Ester maximum decomposition rate T (°C)

pDCPD 212.16 450.97 474.41 --

pDCPD-OH 187.73 230.05 469.93 --

pDCPD-OAc 228.71 252.96 471.12 261.74

pDCPD-OBz 212.82 218.95 473.75 231.10

pDCPD-OMe 180.95 217.05 463.40 --

pDCPD-OPr 219.44 253.76 467.09 --

pDCPD-OOc 196.91 250.02 466.72 --

Figure 36: TGA of pDCPD after 2 hours of curing.

42

Figure 37: TGA of pDCPD-OH after 2 hours of curing.

43

Figure 38: TGA of pDCPC-OAc after 2 hours of curing.

44

Figure 39: TGA of pDCPC-OBz after 2 hours of curing.

45

Figure 40: TGA of pDCPC-OMe after 2 hours of curing.

46

Figure 41: TGA of pDCPD-OPr after 2 hours of curing.

47

Figure 42: TGA of pDCPD-OOc after 2 hours of curing.

48

Figure 43: DSC curve for pDCPD.

49

Figure 44: DSC curve for pDCPD-OR (OR= -OH, -OMe, -OPr and -OBz).

50

Ext ra po l. Pea k 73. 35 °CExt ra po l. Pea k 68. 48 °CExt ra po l. Pea k 64. 62 °C

O nse t 59. 33 °CO nse t 62. 14 °CO nse t 64. 06 °C

10 Hz: DCPD1E' (Modu lus)DCPD1, Le ngth 10.0000 m m , Wid th 9 .9000 m m, Th ick ne ss 0 .9900 m m, Ge om etry fa cto r 104 .1020e+03 1/m

1 Hz: DCPD1E' (Modu lus)DCPD1, Le ngth 10.0000 m m , Wid th 9 .9000 m m, Th ick ne ss 0 .9900 m m, Ge om etry fa cto r 104 .1020e+03 1/m

0.1 Hz: DCPD1E' (Modu lus)DCPD1, Le ngth 10.0000 m m , Wid th 9 .9000 m m, Th ick ne ss 0 .9900 m m, Ge om etry fa cto r 104 .1020e+03 1/m

MPa200

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64


0.2

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64S T A R e S W 1 4 .0 0L a b : M E T T L E R

Figure 45: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD.

51

Ext ra po l. Pea k 91. 34 °C

Ext ra po l. Pea k 104 .84 °C


O nse t 87. 92 °CO nse t 92. 46 °CO nse t 95. 79 °C

10 Hz: DCPDOH2E' (M odu lu s)DCPDOH2, Len gth 1 0.0 00 0 m m , Width 9 .99 00 m m, Th ick ne ss 0.9 80 0 m m , Geo me try fac to r 10 6.354 6e +0 3 1 /m

1 Hz : DCPDOH2E' (M odu lu s)DCPDOH2, Len gth 1 0.0 00 0 m m , Width 9 .99 00 m m, Th ick ne ss 0.9 80 0 m m , Geo me try fac to r 10 6.354 6e +0 3 1 /m

0.1 Hz: DCPDOH2E' (M odu lu s)DCPDOH2, Len gth 1 0.0 00 0 m m , Width 9 .99 00 m m, Th ick ne ss 0.9 80 0 m m , Geo me try fac to r 10 6.354 6e +0 3 1 /m

MPa500

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74




0.5

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74S T A R e S W 1 4 .0 0L a b : M E T T L E R

Figure 46: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OH.

52

Onse t 59.23 °COnse t 60.31 °COnse t 60.21 °C 10 Hz: DCPDOAc3

E' (Modu lus)DCPDOAc3, Le ng th 10.0000 mm , Wid th 9.9900 m m , Th ick ne ss 0 .9800 m m, Ge om etry facto r 106 .3546e+03 1/m

1 Hz: DCPDOAc3E' (Modu lus)DCPDOAc3, Le ng th 10.0000 mm , Wid th 9.9900 m m , Th ick ne ss 0 .9800 m m, Ge om etry facto r 106 .3546e+03 1/m

0.1 Hz: DCPDOAc3E' (Modu lus)DCPDOAc3, Le ng th 10.0000 mm , Wid th 9.9900 m m , Th ick ne ss 0 .9800 m m, Ge om etry facto r 106 .3546e+03 1/m

MPa500

min

°C25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50


1

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

1 0 H z: D C P D O A c3 2 7 .0 1 .2 0 1 6 1 5 : 5 2 : 3 9

S T A R e S W 1 4 .0 0L a b : M E T T L E R

Figure 47: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OAc.

53

Figure 48: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OBz.

O nse t 50. 94 °C

O nse t 54. 94 °CO nse t 59. 62 °C

10 Hz: DCPDCOOPhE' (Modu lus)DCPDCOOPh, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

1 Hz: DCPDCOOPhE' (Modu lus)DCPDCOOPh, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

0.1 Hz: DCPDCOOPhE' (Modu lus)DCPDCOOPh, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

MPa500

min

°C25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

? Extra po l. Pea k 77. 53 °C? Extra po l. Pea k 75. 52 °C? Extra po l. Pea k 68. 94 °C

5

min

°C25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

1 0 H z: D C P D C O O P h 0 7 .0 2 .2 0 1 6 1 1 : 3 1 : 4 9


54

Figure 49: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OMe.

? O nse t 50. 31 °C

? O nse t 55. 79 °C? O nse t 54. 91 °C

10 Hz: DCPDOMe 070216E' (Modu lus)DCPDOMe 070216, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

1 Hz: DCPDOMe 070216E' (Modu lus)DCPDOMe 070216, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

0.1 Hz: DCPDOMe 070216E' (Modu lus)DCPDOMe 070216, L ength 10.0000 m m , Width 9 .9000 m m, Th ickness 0.9900 mm , Geome try fa cto r 104.1020e +03 1 /m

MPa

0

100

200

300

400

min

°C25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40

? Extra po l. Pea k 75. 14 °C? Extra po l. Pea k 75. 08 °C? Extra po l. Pea k 69. 32 °C

0 .0

0 .5

1 .0

1 .5

2 .0

2 .5

min

°C30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40S T A R e S W 1 4 .0 0L a b : M E T T L E R

55

Figure 50: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OPr.

Ex trapo l. Peak 59.34 °CEx trapo l. Peak 56.31 °C

Ex trapo l. Peak 52.90 °C

Onse t 49.69 °COnse t 50.68 °COnse t 50.19 °C

10 Hz: DM PD-OPr-ne w1E' (M odu lu s)DM PD-OPr-new1, Le ng th 1 0.000 0 mm , Wid th 10.00 00 mm , Thi ckn es s 1 .1 000 m m, Ge om etry fac tor 75 .13 15 e+0 3 1/m

1 Hz : DM PD-OPr-new1E' (M odu lu s)DM PD-OPr-new1, Le ng th 1 0.000 0 mm , Wid th 10.00 00 mm , Thi ckn es s 1 .1 000 m m, Ge om etry fac tor 75 .13 15 e+0 3 1/m

0.1 Hz: DM PD-OPr-n ew1E' (M odu lu s)DM PD-OPr-new1, Le ng th 1 0.000 0 mm , Wid th 10.00 00 mm , Thi ckn es s 1 .1 000 m m, Ge om etry fac tor 75 .13 15 e+0 3 1/m

MPa1000

min

°C22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34

? Ex tr apo l. Peak 73.65 °C



min

°C26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34

2


56

Figure 51: DMA storage tensile modulus E′ and mechanical loss factor tan as a function of temperature for pDCPD-OOc.

Wetting Experiment: Polymers were prepared in a 4 ml glass vial. After polymerization was complete the vial was broken and the polymer removed. 30 l deionized water were added to the top of each of the polymers and a snapshot was taken after a few minutes. The copolymer was prepared by mixing DCPD-OH and DCPD-OPr in a 50/50 ratio and following the general polymerization procedure. The lines are visual aids, the differences in the contact angles are quite apparent.

p-DCPD-OH - 37º copolymer - 44º p-DCPD-OPr - 61º

Figure 52: Picture of wetting experiment to understand the hydrophilic and hydrophobic nature of the polymers.

O nse t -9 . 56 °C

O nse t -17 .38 °CO nse t -14 .20 °C

10 Hz: DCP -Ooct-7aE' (Modu lus)DCP-Ooct-7a, L ength 10.0000 m m , Width 9 .9800 m m, Th ickness 0.9800 mm , Geome try fa cto r 106.4612e +03 1 /m

1 Hz: DCP-Ooct-7aE' (Modu lus)DCP-Ooct-7a, L ength 10.0000 m m , Width 9 .9800 m m, Th ickness 0.9800 mm , Geome try fa cto r 106.4612e +03 1 /m

0.1 Hz: DCP -Ooct-7aE' (Modu lus)DCP-Ooct-7a, L ength 10.0000 m m , Width 9 .9800 m m, Th ickness 0.9800 mm , Geome try fa cto r 106.4612e +03 1 /m

MPa2000

min

°C-100 -95 -90 -85 -80 -75 -70 -65 -60 -55 -50 -45 -40 -35 -30 -25 -20 -15 -10 -5 -0

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

? Extra po l. Pea k -2 . 71 °C? Extra po l. Pea k -10 .24 °C

1

min

°C-95 -90 -85 -80 -75 -70 -65 -60 -55 -50 -45 -40 -35 -30 -25 -20 -15 -10 -5 0

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

1 0 H z: D C P - O o ct - 7 a 0 3 .0 2 .2 0 1 6 1 1 : 2 8 : 5 5


57

Figure 53: FTIR for DCPD-OH (2) monomer.

58

Figure 54: FTIR for DCPD-OAc (3a) monomer.

59

Figure 55: FTIR for DCPD-OPr (4b) monomer

60

General procedure for polymer thin films:

20mg of monomer were mixed with 0.03mg of ruthenium catalyst dissolved in 30μL of dry CH2Cl2. The mixture was transferred onto microscope slide and was covered with second slide. Air bubbles were removed by applying pressure on the slides.

For linear polymer films: Grubbs 1st generation catalyst was used. The setup was kept at RT for 2 hours.

For cross-linked polymer films: Grubbs 2nd generation catalyst was used. The setup was kept at 70°C for 30 minutes.

Figure 56: FTIR for the pDCPD-OH thin film.

61

Figure 57: FTIR for the pDCPD-OAc thin film.

62

Figure 58: FTIR for the pDCPD-OPr thin film.

63

Figure 59: FTIR for the linear pDCPD-OAc thin film.

64

Figure 60: FTIR for the linear pDCPD-OPr thin film.

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