Thermo-mechanical Formation-Structure-Prperty Relationships in Photopolymerized Copper-Catalyzed Azide-Alkyne (CuAAC) Networks

Transcription

1 Thermo-mechanical Formation-Structure-Prperty Relationships in Photopolymerized Copper-Catalyzed Azide-Alkyne (CuAAC) Networks Austin Baranek, Han Byul Song, Mathew McBride, Patricia Finnegan, Christopher N. Bowman Supporting Information. 1 H-NMR and 13 C-NMR spectra of the synthesized monomers accompanied by the chemical structure are shown in Figures S1-S12. NMR measurements were performed to determine the purity and degree of functionalization of the synthesized molecules. The number of transients for 1 H and 13 C are 16 and 256, respectively, and a relaxation time of 1 s was used for the integrated intensity determination of 1 H NMR spectra. Shown in Figures S13-S16 are pre and post grazing-angle attenuated total reflectance mode FTIR (gatr-ftir) spectra highlighting the azide peak in the absorption range between cm -1. These experiments provide an indication of the functional group conversions using an air-circulating oven to anneal. Spectra were collected with a resolution of 4 cm -1 by accumulating a minimum of 64 scans per sample. A variety of dynamic mechanical analysis (DMA) experiments were performed on several samples. Figures S17-S20 show the progression of the DMA curves with samples irradiated and annealed only at room temperature. For each consecutive cycle within the DMA (0 C-150 C) the tan δ increases as a result of increased conversion and the increase in the triazole content. Figure S21 shows the resulting mechanical properties of a CuAAC resin initiated with an amine as oppose to a photoinitiator. An additional comparison between analogous networks polymerized using thiol-ene Vs CuAAC is shown in Figure S22. Lastly, Figures S23-S25 show DMA results of off stoichiometric resins to mimic controlled conversions of the CuAAC polymerization and observe the buildup of material properties as conversion increases. All DMA experiment were performed in tension film mode with a heating rate of 3 C min -1 to a maximum temperature of 150 C at a frequency of 1 Hz.

2 Figure S1. 1 H-NMR and 13 C-NMR of bis(6-azidohexyl) (cyclohexane-1,3- diylbis(methylene))dicarbamate (AZ-1). 1 H NMR (CDCl 3 ), ppm: δ (26H, m, CH 2, CH), 3.04 (4H, t, CH 2 carbamate), 3.29 (4H, t, CH 2 N 3 ), 4.06 (4H, t, CH 2 carbamate), 4.76 (2H, s, NH, carbamate); 13 C NMR (CDCl 3 ), ppm: δ 25.19, 25.50, 26.40, 28.75, 28.91, 30.42, (12C, CH 2 ), (2C, CH), (2C, CH 2 -NH, carbamate), (2C, CH 2 -N 3 ), (2C, CH 2 -, carbamate), (2C, C=, carbamate)

3 Figure S2. 1 H-NMR and 13 C-NMR of bis(6-azidohexyl) (1,3-phenylenebis(propane-2,2- diyl))dicarbamate (AZ-2): 1 H NMR (CDCl 3 ), ppm: δ (28H, m, CH 2, CH 3 ), 3.28 (4H, t, CH 2 N 3 ), 3.99 (4H, t, CH 2 carbamate), 5.10 (2H, s, NH, carbamate), 7.30 (3H, s, CH-aromatic), 7.44 (1H, s, CH-aromatic); 13 C NMR (CDCl 3 ), ppm: δ 25.46, 26.36, 28.89, (8C, CH 2 ), (4C, CH 3 ), (2C, CH 2 -N 3 ), (2C, C, aliphatic), (2C, CH 2 -, carbamate), , , (4C, CH, aromatic), (2C, C, aromatic) (2C, C=, carbamate)

4 Figure S3. 1 H-NMR and 13 C-NMR of bis(6-azidohexyl) (methylenebis(cyclohexane-4,1- diyl))dicarbamate (AZ-3): 1 H NMR (CDCl 3 ), ppm: δ (36H, m, CH 2, CH), 3.25 (4H, t, CH 2 N 3 ), 3.27, 3.75 [Mixture of isomers] (2H, s, NH, carbamate), 4.02 (4H, t, CH 2 carbamate), 4.60, 4.83 [Mixture of isomers] (2H, CH-NH); 13 C NMR (CDCl 3 ), ppm: δ 25.49, 26.38, 28.02, 28.72, 28.90, 29.68, 32.00, 32.55, 33.41, 33.60, [Mixture if isomers] (18C, CH, CH 2 ), (1C, cyclohex-ch 2 -cyclohex), (2C, CH 2 -N 3 ), (2C, CH-NH, carbamate), (2C, CH 2 -, carbamate), (2C, C=, carbamate)

5 Figure S4. 1 H-NMR and 13 C-NMR of bis(6-azidohexyl) (methylenebis(4,1- phenylene))dicarbamate (AZ-4): 1 H NMR (CDCl 3 ), ppm: δ (16H, m, CH 2 ), 3.29 (4H, t, CH 2 N 3 ) 3.91 (2H, s, Aryl-CH 2 -Aryl), 4.17 (4H, t, CH 2 -, carbamate), 6.63 (2H, s, CH 2 -NH, carbamate), 7.12 (4H, d, CH-aromatic), 7.31 (4H, d, CH-aromatic); 13 C NMR (CDCl 3 ), ppm: δ 25.50, 26.39, 28.75, (8C, CH 2 ), (1C, Aryl-CH 2 - Aryl), (2C, CH 2 -N 3 ), (2C, CH 2 -, carbamate), , (8C, CH, aromatic), , (4C, C, aromatic) (2C, C=, carbamate)

6 Figure S5. 1 H-NMR and 13 C-NMR of 1-(prop-2-yn-1-yloxy)-2,2-bis((prop-2-yn-1- yloxy)methyl)butane (AL-1): 1 H NMR (CDCl 3 ), ppm: δ 0.90 (3H, t, CH 3 ), 1.45 (2H, q, CH 2 CH 3 ) 2.42 (3H, t, alkyne-h), 3.43 (6H, s, CH 2 ), 4.14 (6H, d, CH 2 -alkyne); 13 C NMR (CDCl 3 ), ppm: δ 7.48 (1C, CH 3 ), (1C, CH 2 ), (1C, C, core), (3C, CH 2 -alkyne), (3C, CH 2 ), (3C, CH, alkyne) (3C, C, alkyne)

7 Figure S6. 1 H-NMR and 13 C-NMR of 1,3,5-tris((prop-2-yn-1-yloxy)methyl)benzene (AL- 2): 1 H NMR (CDCl 3 ), ppm: δ 2.50 (3H, t, CH, alkyne), 4.21 (6H, d, CH 2 -alkyne), 4.63 (6H, CH 2 -aromatic) 7.32 (3H, CH, aromatic); 13 C NMR (CDCl 3 ), ppm: δ (3C, CH 2 -alkyne), (3C, CH 2 -), (3C, CH, alkyne), (3C, C, alkyne), (3C, CH, aromaric), (3C, C, aromatic)

8 Figure S7. 1 H-NMR and 13 C-NMR of 1,3,5-tris(prop-2-yn-1-yloxy)benzene (AL-3): 1 H NMR (CDCl 3 ), ppm: δ 2.56 (3H, t, CH, alkyne), 4.67 (6H, d, CH 2 -alkyne), 6.29 (3H, CH, aromatic); 13 C NMR (CDCl 3 ), ppm: δ (3C, CH 2 -alkyne), (3C, CH, alkyne) (3C, C, alkyne), (3C, CH, aromaric), (3C, C, aromatic)

9 Figure S8. 1 H-NMR and 13 C-NMR of 3,3-bis((prop-2-yn-1-yloxy)methyl)heptane (AL- 4): 1 H NMR (CDCl 3 ), ppm: δ 0.84, 0.92 (6H, t, CH 3 ), 1.29 (8H, m, CH 2 ) 2.41 (3H, t, alkyne-h), 3.33 (4H, s, CH 2 ), 4.14 (4H, d, CH 2 -alkyne); 13 C NMR (CDCl 3 ), ppm: δ 7.23 (1C, CH 3 ), (1C, CH 3 ), 23.54, 23.67, 25.81, (4C, CH 2 ), (1C, C, core), (2C, CH 2 -alkyne), (2C, CH, alkyne) (2C, CH 2 ), (2C, C, alkyne)

10 Figure S9. 1 H-NMR and 13 C-NMR of bis(6-mercaptohexyl) (1,3-phenylenebis(propane- 2,2-diyl))dicarbamate (2-SH) 1 H NMR (CDCl 3 ), ppm: δ (30H, m, CH 2, CH 3, SH), 2.53 (4H, q, CH 2 SH), 3.99 (4H, t, CH 2 carbamate), 5.07 (2H, s, NH, carbamate), 7.30 (3H, s, CH-aromatic), 7.44 (1H, s, CH-aromatic); 13 C NMR (CDCl 3 ), ppm: δ 24.53, 25.36, 27.96, 28.92, (10C, CH 2 ), (4C, CH 3 ), (2C, C-NH, carbamate), (2C, CH 2 -, carbamate), , , (4C, CH, aromatic), (2C, C, aromatic) (2C, C=, carbamate)

11 Figure S10. 1 H-NMR and 13 C-NMR of 1-(allyloxy)-2,2-bis((allyloxy)methyl)butane (1- ene) 1 H NMR (CDCl 3 ), ppm: δ 0.88 (3H, t, CH 3 ), 1.46 (2H, q, CH 2 CH 3 ), 3.35 (6H, s, CH 2 ), 3.97 (6H, 2t, CH 2 -alkene), (6H, m, CH 2, alkene), (3H, m, CH, alkene); 13 C NMR (CDCl 3 ), ppm: δ 7.72 (1C, CH 3 ), (1C, CH 2 ), (1C, C, core), (3C, CH 2 -alkene), (3C, CH 2 -), (3C, CH 2, alkene) (3C, CH, alkene)

12 Figure S11. 1 H-NMR and 13 C-NMR of 1,3,5-tris((allyloxy)methyl)benzene (2-ene): 1 H NMR (CDCl 3 ), ppm: δ 4.05, 4.07 (6H, t, CH 2 ), 4.55 (6H, s, CH 2 ), (6H, CH 2 -alkene) 5.97 (3H, m, CH, alkene) 7.29 (3H, s, CH-aromatic); 13 C NMR (CDCl 3 ), ppm: δ 71.28, (6C, CH 2 ), (3C, CH 2 -ene), (3C, CH, aromatic), (3C, CH-ene), (3C, C, aromatic)

13 Figure S12. 1 H-NMR and 13 C-NMR of Bis(4-((8-azidooctyl)oxy)phenyl)methane (AZ-4- ether) 1 H NMR (CDCl 3 ), ppm: δ (24H, m, CH 2 ), 3.29 (4H, t, CH 2 N 3 ) 3.89 (2H, s, Aryl-CH 2 -Aryl), 3.95 (4H, t, CH 2 -), 6.84 (4H, d, CH-aromatic), 7.11 (4H, d, CH-aromatic); 13 C NMR (CDCl 3 ), ppm: δ 26.00, 26.67, 28.84, 29.10, 29.25, (12C, CH 2 ), (1C, Aryl-CH 2 -Aryl), (2C, CH 2 -N 3 ), (2C, CH 2 -), , (8C, CH, aromatic), , (4C, C, aromatic)

14 Figure S13. FTIR spectra of resin composed of monomers AZ-1 and AL-1 with 2 mol% CuCl 2 [PMDETA], 4 mol% DMPA, and the polymer network cured with 10 mw/cm 2 UV light followed by annealing at 70 C for 24h. The azide peak at 2100 cm -1 (highlighted above) shows to significantly reduce indicting high conversion of the CuAAC polymerization.

15 Figure S14. FTIR spectra of resin composed of monomers AZ-2 and AL-1 with 2 mol% CuCl 2 [PMDETA], 4 mol% DMPA, and the polymer network cured with 10 mw/cm 2 UV light followed by annealing at 70 C for 24h. The azide peak at 2100 cm -1 (highlighted above) shows to significantly reduce indicting high conversion of the CuAAC polymerization.

16 Figure S15. FTIR spectra of resin composed of monomers AZ-3 and AL-1 with 2 mol% CuCl 2 [PMDETA], 4 mol% DMPA, and the polymer network cured with 10 mw/cm 2 UV light followed by annealing at 70 C for 24h. The azide peak at 2100 cm -1 (highlighted above) shows to significantly reduce indicting high conversion of the CuAAC polymerization.

17 Figure S16. FTIR spectra of resin composed of monomers AZ-4 and AL-1 with 2 mol% CuCl 2 [PMDETA], 4 mol% DMPA, and the polymer network cured with 10 mw/cm 2 UV light followed by annealing at 70 C for 24h. The azide peak at 2100 cm -1 (highlighted above) shows to significantly reduce indicting high conversion of the CuAAC polymerization.

18 Figure S17. Plots of storage modulus vs temperature and tan δ vs. temperature for a single resin formulation composed of azide monomers (AZ-1) with the alkyne crosslinker (AL-1). The resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% DMPA and were cured with 10 mw/cm 2 UV light. The film was annealed at room temperature for 24h followed by three consecutive DMA cycles from 0 C-150 C. Figure S18. Plots of storage modulus vs temperature and tan δ vs. temperature for a single resin formulation composed of azide monomers (AZ-2) with the alkyne crosslinker (AL-1). The resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% DMPA and were cured with 10 mw/cm 2 UV light. The film was annealed at room temperature for 24h followed by three consecutive DMA cycles from 0 C-150 C.

19 Figure S19. Plots of storage modulus vs temperature and tan δ vs. temperature for a single resin formulation composed of azide monomers (AZ-3) with the alkyne crosslinker (AL-1). The resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% DMPA and were cured with 10 mw/cm 2 UV light. The film was annealed at room temperature for 24h followed by three consecutive DMA cycles from 0 C-150 C. Figure S20. Plots of storage modulus vs temperature and tan δ vs. temperature for a single resin formulation composed of azide monomers (AZ-4) with the alkyne crosslinker (AL-1). The resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% DMPA and were cured with 10 mw/cm 2 UV light. The film was annealed at room temperature for 24h followed by three consecutive DMA cycles from 0 C-150 C.

20 Figure S21. Plots of storage modulus and tan δ vs. temperature for a single resin formulation composed of azide monomers (AZ-2) with the alkyne crosslinker (AL-1). The resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% hexylamine. The hexylamine was added immediately before film casting. The film was annealed at 70 C for 24h followed by three consecutive DMA cycles. The storage modulus and tan δ curves shown are of the third cycle within the DMA. NTE: The same resin cured with DMPA is reported as having a T g at 67 C.

21 Thiol-ene - Thioether linkage S S S 2-ene S S S S S S S S S HS 2-SH N H N H SH CuAAC - Triazole linkage AL-2 N NN N N N N N N N N NNN NNN N N N N NN N N N N NN N N NN N N N Figure S22. Plots of tan δ vs temperature and storage modulus vs. temperature for analogous materials made from either the thiol-ene or CuAAC reactions and the generalized polymeric structure. The thiol-ene resin composed 4 mol% DMPA and the CuAAC resin composed 2 mol% CuCl 2 [PMDETA] and 4 mol% DMPA, and both were cured with 10 mw/cm 2 UV light. Representative curves are presented as the third cycle in the DMA. N 3 AZ-2 N H N H N 3

22 Figure S23. Plot of storage modulus and tan δ vs. temperature for an off stoichiometric resin composed of 1 eq AZ-2, 0.25 eq AL-1 and 0.5 eq AL-4 based on moles of functional groups providing a theoretical azide conversion of 75%. Resins were cured using 5-10 mw/cm 2 of UV irritation for 5 min followed by post cure at 70 C for 24 hours. FTIR using a Nicolet 8700 incorporated with a heating stage at 70 C was used to monitor the polymerization conversions of the functional groups in transmission mode and it was determined that 74% of the azides reacted and ~100% of the alkynes reacted. DMA is represented as the 3 rd scan.

23 Figure S24. Plot of storage modulus and tan δ vs. temperature for an off stoichiometric resin composed of 1 eq AZ-2, 0.4 eq AL-1 and 0.4 eq AL-4 based on moles of functional groups providing a theoretical azide conversion of 80%. Resins were cured using 5-10 mw/cm 2 of UV irritation for 5 min followed by post cure at 70 C for 24 hours. FTIR using a Nicolet 8700 incorporated with a heating stage at 70 C was used to monitor the polymerization conversions of the functional groups in transmission mode and it was determined that 83% of the azides reacted and ~100% of the alkynes reacted. DMA is represented as the 3 rd scan.

24 Figure S25. Plot of storage modulus and tan δ vs. temperature for an off stoichiometric resin composed of 1 eq AZ-2, 0.7 eq AL-1 and 0.2 eq AL-4 based on moles of functional groups providing a theoretical azide conversion of 90%. Resins were cured using 5-10 mw/cm 2 of UV irritation for 5 min followed by post cure at 70 C for 24 hours. FTIR using a Nicolet 8700 incorporated with a heating stage at 70 C was used to monitor the polymerization conversions of the functional groups in transmission mode and it was determined that 91% of the azides reacted and ~100% of the alkynes reacted. DMA is represented as the 3 rd scan.