Silane-Acrylate Chemistry for Regulating Network. Formation in Radical Photopolymerization

Transcription

1 Supporting Information for: Silane-Acrylate Chemistry for Regulating Network Formation in Radical Photopolymerization Johannes Steindl,, Thomas Koch, Norbert Moszner, and Christian Gorsche *,, Institute of Applied Synthetic Chemistry, Technische Universität Wien, Getreidemarkt 9/163 MC, 1060 Vienna, Austria Christian-Doppler-Laboratory for Photopolymers in Digital and Restorative Dentistry, Getreidemarkt 9, 1060 Vienna, Austria Institute of Materials Science and Technology, Technische Universität Wien, Getreidemarkt 9/308, 1060 Vienna, Austria Ivoclar Vivadent AG, 9494 Schaan, Liechtenstein *corresponding author: Contents: Figure S1. Figure S2. Figure S3. Figure S4. Figure S5. Table S1. Table S2. Table S3. Table S4. Figure S6. 1 H NMR spectrum of DSiH. 13 C NMR spectrum of DSiH 29 Si INEPT NMR spectrum of DSiH. Double bond (green, filled) and silane conversion (blue, patterned) of photopolymerization reactions with monomer (a) BA, equimolar mixture of BA and silane (i.e. TTMSSiH or DSiH); (b) BMA series; (c) VB series; (d) NAM series. 1 H NMR spectra of D3A/DSiH 20DB before (black) and after a storage period of 64 d (red). Photo DSC results for D3A (reference) and formulations with chain transfer agent (i.e. silane DSiH and thiol DSH; 5, 20 and 50 mol% respectively). RT-NIR-photorheology results for D3A (reference) and formulations with CTA (i.e. thiol DSH and silane DSiH). DMTA results for polyd3a and photopolymers with CTA (i.e. thiol DSH and silane DSiH). Tensile test results for polyd3a and photopolymers with CTA (i.e. thiol DSH and silane DSiH). TGA plots for reference polyd3a (solid), polyd3a/dsh 5 (dash dot dot), 20 (dash dot), polyd3a/dsih 5 (short dash) and 20 (dash). S1

2 1. 1 H, 13 C and 29 Si NMR spectra of 2,2,15,15-tetramethyl-3,14-bis(trimethylsilyl)-6,11- dioxa-2,3,14,15-tetrasilahexadecane DSiH Figure S1. 1 H NMR spectrum of DSiH. S2

3 Figure S2. 13 C NMR spectrum of DSiH. S3

4 Figure S3. 29 Si INEPT NMR spectrum of DSiH. S4

5 2. Conversion analysis via 1 H NMR spectroscopy The conversion of the silane-ene reactions were determined by 1 H NMR spectroscopic analysis. A detailed procedure for the respective NMR spectra evaluation has been published previously and DSiH-based formulations were analyzed and evaluated accordingly. 1 Figure S4. Double bond (green, solid) and silane conversion (blue, striped) of photopolymerization reactions (a) with neat monomer BA and equimolar mixtures with silane (i.e. TTMSSiH or DSiH); (b) BMA series; (c) VB series; (d) NAM series. S5

6 3. Storage stability of silane-acrylate formulations Figure S5. 1 H NMR spectra of D3A/DSiH 20 mol% before (black) and after a storage period of 64 d (red). 4. Photo-DSC Table S1. Photo DSC results for D3A (reference) and formulations with chain transfer agent (i.e. silane DSiH and thiol DSH; 5, 20 and 50 mol% respectively). Formulation ΔH tmax t95% / J g -1 / s / s D3A 472 ± ± ± 1 D3A/DSH ± ± ± 1 D3A/DSH ± ± ± 1 D3A/DSH ± ± ± 1 D3A/DSiH ± ± ± 1 D3A/DSiH ± ± ± 1 D3A/DSiH ± ± ± 2 ΔH measured heat of polymerization t max time to maximum of polymerization rate t 95% time to 95% of heat evolution S6

7 5. RT-NIR-photorheology Table S2. RT-NIR-photorheology results for D3A (reference) and formulations with CTA (i.e. thiol DSH and silane DSiH). Formulation G'final / MPa tgel / s DBCgel / % DBCfinal / % D3A 0.63 ± ± ± 1 93 ± ± 0 D3A/DSH ± ± ± 1 95 ± 1 90 ± 1 D3A/DSH ± ± ± 3 > ± 3 D3A/DSH ± ± ± 6 > ± 2 D3A/DSiH ± ± ± 1 95 ± 1 84 ± 2 D3A/DSiH ± ± ± 4 97 ± 1 65 ± 4 D3A/DSiH ± ± ± 2 97 ± 2 26 ± 4 G' final final storage modulus t gel time to gel point DBC gel double bond conversion at gel point DBC final final double bond conversion FN measured normal force 6. DMTA Table S3. DMTA results for polyd3a and photopolymers with CTA (i.e. thiol DSH and silane DSiH). 7. Tensile test Photopolymer G'20 Tg fwhm G'r / MPa / C / C / MPa polyd3a polyd3a/dsh polyd3a/dsh polyd3a/dsih polyd3a/dsih G' 20 storage modulus G' measured at 20 C T g glass transition temperature fwhm full width at half maximum of the loss factor peak at T g G'r storage modulus G' measured at Tg + 20 C Table S4. Tensile test results for polyd3a and photopolymers with CTA (i.e. thiol DSH and silane DSiH). Photopolymer σmax / N mm -2 elongation at break / % polyd3a 24.8 ± ± 2.4 polyd3a/dsh ± ± 0.9 polyd3a/dsh ± ± 3.7 polyd3a/dsih ± ± 2.8 polyd3a/dsih ± ± 2.3 σ max maximum stress FN / % S7

8 8. TGA TGA measurements were performed on a Netzsch F1 Jupiter 449 thermal analysis instrument. Approximately 10 mg of sample (derived from DMTA specimen) were weighed into an aluminum pan. The measurements were conducted at a nitrogen flow rate of 40 ml min -1 and a heating rate of 10 C min -1. Figure S6. TGA plots for reference polyd3a (solid), polyd3a/dsh 5 (dash dot dot), 20 (dash dot), polyd3a/dsih 5 (short dash) and 20 (dash). References 1. Steindl, J.; Svirkova, A.; Marchetti-Deschmann, M.; Moszner, N.; Gorsche, C. Light-Triggered Radical Silane-Ene Chemistry Using a Monosubstituted Bis(trimethylsilyl)silane. Macromol. Chem. Phys. 2017, 218, /macp S8