UV-Induced Self-Repairing Polydimethylsiloxane-Polyurethane (PDMS-PUR) Cu- Catalyzed Networks

Transcription

1 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 * - orresponding uthor (e-mil: mreku@lemson.edu)

2 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 : The verge moleulr weight of PDMS ws determined y rtioing :=4:61.72 nd numer of repeting units n= =10.3, giving M n =

3 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.

4 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.

5 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.

6 Figure S5 A - Shemeti representtion of two struture of opper hloride. B - Trnsverse nd longitudinl virtionl modes of Cu-Cl onds.

7 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.

8 & + A1 B Wvenumer3(m 51 ) Wvenumer3(m 51 ) Wvenumer3(m 51 ) Wvenumer+(m 51 ) A2 B Wvenumer0(m ) Wvenumer&(m 21 ) Wvenumer0(m 21 ) Wvenumer0(m 21 ) A3 B Wvenumer1(m 31 ) Wvenumer1(m 31 ) Wvenumer2(m 41 ) Wvenumer2(m 41 ) Figure S7. Rmn spetr of PDMS-PUR networks in the , nd 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 ().

9 ( ) A1 B1 541 A Wvenumer1(m 31 ) Wvenumer2(m 41 ) B Wvenumer)(m 31 ) Wvenumer1(m 41 ) Wvenumer0(m 21 ) Wvenumer0(m 21 ) A3 B Wvenumer2(m 41 ) Wvenumer((m 41 ) Figure S8. Rmn spetr of PEG-PUR networks in the , , nd 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 ().