Eletroni Supplementry Mteril (ESI) for Journl of Mterils Chemistry A. This journl is The Royl Soiety of Chemistry 2014 Supporting Online Mterils UV-Indued Self-Repiring Polydimethylsiloxne-Polyurethne (PDMS-PUR) Cu- Ctlyzed Networks Zhnhu Wng, Ying Yng, Rusln Burtovyy, Igor Luzinov nd Mrek W. Urn* Deprtment of Mterils Siene nd Engineering, 299A Sirrine Hll Clemson University Clemson, SC 29634-0971 * - orresponding uthor (e-mil: mreku@lemson.edu)
Figure S1. NMR spetr of PDMS In order to determine the numer of repeted units in PDMS, 1 H NMR spetr shown in Figure S1 were reoreded. The re rtios for H nd H resonnes ws determined to e 4 : 61.72. The verge moleulr weight of PDMS ws determined y rtioing :=4:61.72 nd numer of repeting units n=61.72 6=10.3, giving M n = 877.2.
Figure S2. NMR spetr of HDI In order to determine the omposition of the isoynte, 1 H NMR spetrum ws reorded shown in Figure S2. The re rtio of H : H : H : d H = 2 : 2.75 : 2.75 : 1, inditing 2:3 rtio of mono-hdi nd tri-hdi in the omposition with no presene of di-hdi.
Figure S3 ATR-IR spetr of: - CuCl 2, - PDMS, HDI, nd d - PDMS-PUR-CuCl 2 networks. Figure S3 illustrtes ATR-IR spetr of CuCl 2 (), PDMS (), HDI () nd PDMS-PUR- CuCl 2 networks (d). The nds t 1022 nd 1080 m -1 due to symmetri Si-O strething nd 1250 m -1 ttriuted to C-H symmetri deformtions of Si-CH 3 group pper in tre nd, demonstrting tht PDMS is opolymerized into PDMS-PUR-CuCl 2 networks. The symmetri strething virtion t 2268 m -1 nd symmetri strething virtion t 1355 m -1 due to N=C=O funtionlities dispper in tre d, signifying ll NCO groups hve een reted. These oservtions onfirms tht PUR-PDMS-CuCl 2 networks were suessfully synthesized.
Figure S4 Rmn spetr of: - CuCl 2, - CuCl 2 film deposited form DMF, - PDMS- PUR-CuCl 2, nd d - PEG-PUR-CuCl 2 networks. Figure S4 illustrtes Rmn spetr of CuCl 2 (), CuCl 2 lyers deposited form DMF (), PDMS-PUR-CuCl 2 () nd PEG-PUR-CuCl 2 networks (d). The nd t 285 m -1 ttriuted to longitudinl virtions of Cu-Cl onds shifts to lower energy, thus suggesting the CuCl 2 oligomers formtion. The nd t 193 m -1 due to the trnsverse virtions of Cu-Cl onds is deteted in the PDMS-PUR-CuCl 2 network (), while the nd t 285 m -1 diminishes to minimum, mnifesting the formtion of Cu-O oordintion ond. Figure S5 A illustrtes the formtion of CuCl 2 oligomers, nd Figure S5 B shows trnsverse nd longitudinl virtionl modes of Cu-Cl onds deteted in Rmn mesurements.
Figure S5 A - Shemeti representtion of two struture of opper hloride. B - Trnsverse nd longitudinl virtionl modes of Cu-Cl onds.
Figure S6 ATR-IR spetr of: - PEG-PUR-DBTDL, - PDMS-PUR-DBTDL, - PEG- PUR-CuCl 2, nd d - PDMS-PUR-CuCl 2 networks. Figure S6 illustrte ATR-IR spetr of PEG-PUR-DBTDL (), PDMS-PUR-DBTDL (), PEG-PUR-CuCl 2 () nd PDMS-PUR-CuCl 2 (d) networks. The nds t 1097 nd 1093 m -1 due to symmetri virtions of C-O-C entities in PEG re deteted in Tres nd, demonstrting PEG mromonomer inorprtion into PEG-PUR network. The nds t 1080 m -1 nd 1022 m -1 due to symmetri virtions of Si-O-Si in PDMS oserved in Tres nd d demonstrte tht PDMS ws inorprted into PDMS-PUR network.
& + A1 B1 262 240 255 270 285 300 315 Wvenumer3(m 51 ) 262 240 255 270 285 300 315 Wvenumer3(m 51 ) 492 492 160 240 320 400 480 560 160 240 320 400 480 560 Wvenumer3(m 51 ) Wvenumer+(m 51 ) A2 B2 644 644 653 653 635 640 645 650 655 Wvenumer0(m 21 635 640 645 650 655 ) Wvenumer&(m 21 ) 492 492 400 450 500 550 600 650 700 750 400 450 500 550 600 650 700 750 Wvenumer0(m 21 ) Wvenumer0(m 21 ) A3 B3 3278 3150 3225 3300 3375 Wvenumer1(m 31 ) 2909 2909 3278 3150 3225 3300 3375 Wvenumer1(m 31 ) 2850 3000 3150 3300 3450 2850 3000 3150 3300 3450 Wvenumer2(m 41 ) Wvenumer2(m 41 ) Figure S7. Rmn spetr of PDMS-PUR networks in the 120-580, 620-670 nd 2800-3500 m -1 regions olleted from of undmged (A1-A3) nd dmged (B1-B3) res s funtion of UV exposure for 0 h (), 0.5 h (), nd 2 h ().
( ) A1 B1 541 A2 641 541 563 520 560 600 640 680 Wvenumer1(m 31 ) 937 996 920 940 960 980 1000 1020 Wvenumer2(m 41 ) B2 563 520 560 600 640 680 Wvenumer)(m 31 ) 937 996 920 940 960 980 1000 1020 Wvenumer1(m 41 ) 641 900 950 1000 1050 1100 1150 1200 Wvenumer0(m 21 ) 900 950 1000 1050 1100 1150 1200 Wvenumer0(m 21 ) A3 B3 1758 1758 1700 1720 1740 1760 1780 1800 Wvenumer2(m 41 ) 1700 1720 1740 1760 1780 1800 Wvenumer((m 41 ) Figure S8. Rmn spetr of PEG-PUR networks in the 200-600, 900-1200, nd 1600-1900 m -1 regions olleted from undmged (A1-A3) nd dmged (B1-B3) res s funtion of UV exposure for 0 (), 0.5 (), nd 2 hrs ().