1. Gilles Sebea, Xiaosong Wangb
Convenient techniques to characterize the grafting “living” polymerization using cellulose nanocrystals (CNC) initiators
Zhen Zhanga,b
Gilles Sebea, Xiaosong Wangb
a University of Bordeaux, CNRS, LCPO, UMR 5629, F Pessac, France
b Department of Chemistry and Waterloo Institute of Nanotechnology (WIN), University of Waterloo, Waterloo, Canada
International Doctoral School in Functional Materials (IDS-FunMat)

2. Outline 1. Background 2. Preparation of CNC nano-initiator: CNC-Br
3. CNC-g-PS by SI ATRP
4. CNC-g-P4VP by SI ATRP
5. Summary

3. Rod-like nanocrystals
1. Background
Grafting polymer onto the surface of nanoparticles in a controlled way to prepare well designed nanocomposites
Cellulose NanoCrystals (CNC)
Cellulose
Crystallite
Amorphous domain
Wood, plants
Rod-like nanocrystals
(L = nm; Ø = 5-20 nm )
CNC
Acid Hydrolysis
Surface Initiated Atom Transfer Radical Polymerization (SI ATRP)

4. 1. Background CNC-g-polymer
Characterization of grafted polymer: “livingness” of grafted polymers
Cleave the grafted polymer
free polymer initiated by sacrificial initiator
Time consuming & tedious!
Controversial & the substrate matters!

5. 1. Background
Without cleaving, how to characterize the grafted polymers?
The glass transition temperature (Tg) of CNC-g-Polymer by DSC
The hydrodynamic diameter of CNC-g-Polymer by DLS
The weight loss ratio of grafted polymer to CNC by TGA
Separated decomposition temperature between grafted polymer and CNC: PS, PDMAEMA, PMA, PNiPAAm,POEGMA, PtBA
Not well separated: P4VP, PMMAZO
The specific element analysis: N element in P4VP

6. 2. CNC nano-initiator: CNC-Br
FTIR
13C NMR

7. 2. CNC nano-initiator: CNC-Br
XPS
Br content on the surface of CNC-Br:
At.% 2.13% on the surface

8. 2. CNC nano-initiator: CNC-Br
TGA EA
Element
CNC-Br by EA % C
42.7 O
34.3 H
5.2 Br
11.9 N
0.88
DTG
CNC-Br :
(C6H10O5)3.2(C4H6OBr)
Majoinen, J., et al., Biomacromolecules, (8): p

9. 3. CNC-g-PS by SI ATRP SI ATRP of PS on CNC-Br with presence of EBiB
FTIR of CNC-g-PS

10. 3. CNC-g-PS by SI ATRP
Kinetic of free PS
TGA and DTG of free PS

11. 3. CNC-g-PS by SI ATRP TGA and DTG of CNC-g-PS Conclusion:
•The weight loss ratio of grafted PS to CNC-Br by TGA in CNC-g-PS
• Mn of free PS to molecular weight of CNC-Br ratio
Conclusion:
1. Almost all the initiating sites on the surface of CNC-Br were initiated by SI ATRP
2. The grafted PS had the similar Mn with free PS in the SI ATRP system.

12. 3. CNC-g-PS by SI ATRP DLS DSC
The hydrodynamic diameter of CNC-g-PS vs monomer conversion
Tg of free PS and CNC-g-PS vs -105/Mn

13. 4. CNC-g-P4VP by SI ATRP
FTIR
TGA
DTG
Tg by DSC

14. 4. CNC-g-P4VP by SI ATRP EA DP of grafted P4VP was 52
Element
CNC-Br by EA %
CNC-g-P4VP by EA % C
42.7
75.6 O
34.3
4.76 H
5.2
6.66 Br
11.9 - N
0.88
11.97
Suppose all the initiating sites were initiated by SI ATRP of P4VP
DP of grafted P4VP was 52
Theoretical DP of free P4VP calculated by monomer conversion: 57
Conclusion according the comparison of DP:
1. The assumptions that almost all the initiating sites on CNC-Br were initiated was appropriate and
2. The grafted P4VP had the similar Mn with the free P4VP.

15. 5. Summary The preparation of CNC-Br: FTIR, 13C NMR, XPS, TGA, EA
CNC-g-PS: FTIR
Without cleaving grafted PS
the thermal decomposition weight ratio by TGA
Tg by DSC
hydrodynamic diameter by DLS
CNC-g-P4VP: FTIR, TGA, DSC
Without cleaving grafted P4VP
N element content by EA
Almost all the initiating sites on the surface of CNC-Br were initiated by SI ATRP
The grafted polymer on CNC-Br had very similar molecular weight with free polymer in SI ATRP system

16. Thanks for your attention!
Supervisors:
Xiaosong Wang
Gilles Sebe
Committee members：
Michael Tam
Eric Prouzet
John Honek
Colleagues:
Jérémie, Benjamin
Shaowei, Kai, Dapeng, Nimer, Nicholas, Na, Diya, Robert
Zengqian Shi, Zhaolin, Juntao Tang, Nate, Xinyao, Debbie, Li
Other colleagues
Administrative staff.