Byrne, Robert

Diamond, Dermot

Fraser, Kevin J.

Gallagher, Simon

English

Name not available

UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  1 Physico-­‐chemical	  proper0es	  of	  Ionic-­‐Liquid/Water	  Mixtures	  Simon	  Gallagher	  •  UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  2 Contents	  •  Introduction •  Ionic Liquid based Poly(N-­‐Isopropylacrylamide)	  Gels •    Experimental  – Raman Spectroscopy of Ionic Liquid/Water Interactions •  Conclusions •  Acknowledgements Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  3 National Centre for Sensor Research Over 260 f/t researchers and support staff 23 affiliated faculty Investments and income since 1999 now approaching €100 million 1500 m2 well-equipped specialist lab space and offices Phase II expansion completed  2008 (1300 m2) CLARITY The Centre for Sensor Web Technologies Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  4 •   5-year, €16.4 million research program to develop next generation Sensor Web Technologies with significant environmental focus •  Brings together fundamental materials science, functional polymers, device prototyping, energy management, adaptive middleware, wearable sensors, distributed environmental monitoring. www.clarity-centre.org CLARITY – SFI CSET Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  5 Thermo-­‐responsive	  Gels	  • 	  Poly(N-­‐Isopropylacrylamide)	  or	  “PNIPAAM”,	  display	  inverse	  solubility	  upon	  hea0ng.	  • 	  Hydrophilic	  to	  Hydrophobic	  transi0on	  occurs	  at	  lower	  cri0cal	  solu0on	  temperature	  (LCST),	  30-­‐35°C.	  • 	  	  Below	  LCST,	  gel	  swells	  by	  intake	  of	  water	  molecules	  through	  hydra0on	  of	  alipha0c	  groups	  and	  hydrogen	  bonding	  with	  amide	  group.	  • 	  Above	  LCST,	  gel	  collapses	  along	  backbone	  before	  water	  molecules	  are	  expelled,	  process	  is	  driven	  by	  the	  conversion	  from	  polymer-­‐solvent	  bonds	  to	  polymer-­‐polymer	  and	  solvent-­‐solvent	  bonding.1	   1. H.G Shild, Prog. Polym. Sci., Vol. 17, 163-249, 1992  Hydrophilic (below LCST) Hydrophobic (above LCST) ΔT Time CHCH2 *OHNCHH3C CH3CHCH2 *OHNCHH3C CH3Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Triphasic	  PNIPAAM	  System	  • 	  Ionic	  Liquids	  incorporated	  into	  the	  polymer	  forms	  a	  modiﬁed	  triphasic	  system.	  • 	  With	  certain	  Ionic	  Liquids,	  rate	  of	  contrac0on	  can	  be	  manipulated.	  • 	  When	  placed	  in	  water,	  the	  IL	  can	  tune	  the	  LCST	  temperature,	  employing	  plas0sizer	  eﬀect.	  • 	  Also	  improve	  the	  mechanical	  stabilty	  of	  the	  gel.	  	  LCST Polymeric Binding Modified Solvent Structure Ionic Liquid CHCH2 *OHNCHH3C CH3IL Polymer Gels Water Tea Leaves Milk Introduction Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  •  	  1-­‐Ethyl-­‐methyl-­‐3-­‐imidazolium-­‐ethyl	  sulfate;	  [C2mim	  EtSO4]	  	  Ionic	  Liquids	  crosslinked	  w/	  PNIPAAM	  Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  •  1-­‐Ethyl-­‐methyl-­‐3-­‐imidazolium	  Bis(triﬂuoromethylsulfonyl)imide;	  [C2mim	  NTf2]	  Varia0on	  of	  Anion	  for	  Comparison	  Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  •  Trihexyltetradecylphosphonium	  Dicyanamide;	  [P66614][DCA]	  Ionic	  Liquids	  crosslinked	  w/	  PNIPAAM	  Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  PNIPAAM	  (g)	   Ionic	  Liquid	  (g)	   %	  Vol	  change	  a8er	  ~10secs	  	   Flexibility	  (~20°C)	   (~40°C)	  0.5	   1	   56	   ******	   *****	  Manipula0on	  in	  rate	  of	  contrac0on	  •  [C2mim][EtSO4] crosslinked with PNIPAAM monomer submerged in water above LCST   Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Improvement	  in	  mechanical	  stability	  PNIPAAM	  (g)	   Ionic	  Liquid	  (g)	   %	  Vol	  change	  a8er	  ~10secs	  	   Flexibility	  (~20°C)	   (~40°C)	  0.5	   1	   17	   ******	   **	  IL Polymer Gels •  [P66614][DCA] crosslinked with PNIPAAM monomer submerged in water above LCST Introduction Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Raman Spectroscopy of [P6,6,6,14][DCA] & H20 Mixture 0 2 4 6 8 10 12 14 2160 2165 2170 2175 2180 2185 2190 2195 2200 2205 2210 Intensity (%) Wavenumbers (cm-1) P66614 DCA P66614 DCA & WATER - Nitrile stretch at 2188cm-1 shifts upfield to 2191cm-1, increasing in energy   Nitrile stretch @ 2188cm-1 Raman of IL/H2O Introduction IL Polymer Gels Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  -  CH3(N) and CH2(N) stretch at 1022cm-1 increases in energy with the addition of bulk water -  Also a broadening of the peak indicates more solvation  1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 1000 1005 1010 1015 1020 1025 1030 1035 1040 1045 Intensity (%) Wavenumbers (cm-1) C2mim EtSO4 EMIM ETSO4 & WATER Raman of IL/H2O Raman Spectroscopy of [C2mim][EtSO4] & H20 Mixture Introduction IL Polymer Gels Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Raman Spectroscopy of [C2mim][NTf2] & H2O Mixtures 1.9 2.1 2.3 2.5 2.7 2.9 3.1 1000	  1005	  1010	  1015	  1020	  1025	  1030	  1035	  1040	  1045	  1050	  Intensity (%) Wavenumbers (cm-1) C2MIM NTF2 (NEAT) C2MIM NTF2 & H2O Raman of IL/H2O Introduction IL Polymer Gels Conclusions Acknowledgments -  The anion is changed to the more hydrophobic [NTf2]  -  The less significant change shown, displays the effect that bulk water interaction is more apparent in the IL containing the more hydrophillic EtSO4 anion UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  1 2 3 4 5 6 7 8 9 2905 2925 2945 2965 2985 3005 3025 Intensity (%) Wavenumbers (cm-1) EMIM ETSO4 NEAT EMIM ETSO4 & WATER Raman Spectroscopy of [C2mim][EtSO4] & H2O -  Ethyl HCH stretch at 2944cm-1 and 2966cm-1 broadens and shifts in energy due to solvation by bulk water.      Raman of IL/H2O Introduction IL Polymer Gels Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  16 Raman Spectroscopy of [C2mim][NTf2] & H2O Mixtures -  The anion is changed to the more hydrophobic [NTf2]  -  Shown that water has interacted more significantly with the IL containing the more hydrophillic [EtSO4] than the IL containing the hydrophobic [NTf2] Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  17 Raman Spectroscopy [C2mim][EtSO4] & H2O Mixtures -  CH3(N)HCH stretch at 3110cm-1 and ring HCCH stretch at 3166cm-1 -  After addition of bulk water, ratio between peaks increases substantially   Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  18 Raman Spectroscopy of [C2mim][NTf2] & H2O Mixtures -  Changing to the hydrophobic [NTf2] leads to no change in ratio between peaks.  -  Showing again water interaction favours the hydrophillic [EtSO4] Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Conclusions [P66614][DCA]   -  Nitrile group of [P66614][DCA] was found to be affected by bulk water interaction, showing a shift to increase in energy.  [C2mim][EtSO4]   -  IL containing hydrophilic [EtSO4] shows interactions specifically with imidazole ring -  Varying of anion to more hydrophobic [NTF2] shows IL undergoes less change when interacting with water  -  Result shows that the anions in both ILs play a prominent role in Ionic Liquid crosslinked PNIPAAM gel. Introduction IL Polymer Gels Raman of IL/H2O Conclusions Acknowledgments UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  20 Acknowledgments Acknowledgments Prof. Dermot Diamond  Dr. Kevin Fraser  Dr. Robert Byrne Introduction IL Polymer Gels Raman of IL/H2O Conclusions 21 UNIVERSITY COLLEGE DUBLIN      DUBLIN CITY UNIVERSITY      TYNDALL NATIONAL INSTITUTE  Thanks for Listening! 

Physico-chemical properties of ionic-liquid water mixtures

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Physico-chemical properties of ionic-liquid water mixtures

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