1. /Faculty of Chemical Engineering & Chemistry 1 Monitoring Interlayer Formation by Infrared Spectroscopy in Layered Reactive Polymer Blends J. Li a,b, M. Prusty a,c, H. Goossens a,c a Eindhoven University of Technology - Department of Chemical Engineering and Chemistry- Laboratory of Polymer Technology P.O. Box 513, 5600 MB Eindhoven, The Netherlands b Fudan University -Department of Macromolecular Science, 200433 Shanghai, China c Dutch Polymer Institute, P.O. Box 902, 5600 AX Eindhoven, The Netherlands

2. /Faculty of Chemical Engineering & Chemistry 2 Outline  Introduction  Objective  Modification of SAN in solution  On-line Monitoring interlayer reaction by ATR-FTIR in layered reactive polymer blends  Future work

3. /Faculty of Chemical Engineering & Chemistry 3 Introduction Polymer blends : Combination of existing polymers Advantage: Cheap Tuning properties easily high property/cost performances C. Koning, Prog. Pol. Sci (1998), 707 Disadvanatage: Immiscibility Coarse phase morphology

4. /Faculty of Chemical Engineering & Chemistry 4 In situ compatibilization by reactive blending A/B immiscible blend  B - Y A/B X-functionalized A* X-functionalized C* (miscible with A) + “in situ” block or grafted copolymers Y-functionalized B* Y-functionalized D* (miscible with B)

5. /Faculty of Chemical Engineering & Chemistry 5 Introduction Reactive blending: C. Koning, Prog. Pol. Sci (1998), 707 Reactive additive for phase (A) Reactive additive for phase (B) In situ generated copolymer X’X’ Y’ (A)-branch-(B) X Y (A)-graft-(B) X Y X’X’ Y’

6. /Faculty of Chemical Engineering & Chemistry 6 Objective Understand the reactive blending process from a fundamental point of view ---- the competition between processes like diffusion to interface and reaction between the components inside the interface

7. /Faculty of Chemical Engineering & Chemistry 7 Oxazoline: Universal compatibilizer B.M. Culberston, Prog. Pol. Sci (2002), 579 RNH 2 R'CONHCH 2 CH 2 NHR

8. /Faculty of Chemical Engineering & Chemistry 8 Modification of SAN in solution Reaction scheme

9. /Faculty of Chemical Engineering & Chemistry 9 Polymer modification Materials: SAN, AE, catalyst, DCB (solvent) Procedure: Precipitation: 5 wt% of polymer in chloroform and then add to it 10 times methanol Drying: 48 hrs. at 45 °C Parameters: Ratio AN/AE, different catalysts, catalyst concentration, temperature and reaction time.

10. /Faculty of Chemical Engineering & Chemistry 10 Characterization (Mid-IR) Nitrile Oxazoline Phenyl

11. /Faculty of Chemical Engineering & Chemistry 11 Kinetics of solution modification K = 6.4*10 4 exp(-10.2*10 3 /T) ( g/mmol·min)

12. /Faculty of Chemical Engineering & Chemistry 12

13. /Faculty of Chemical Engineering & Chemistry 13 Materials: SAN-oxazoline (1.9 ~5.4 wt% oxazoline) poly (ethylene-co-methacrylic acid) (15 wt% acid) Sample: a: thin film of SAN-oxazoline (100nm~ 400nm) b: thick film of PE-co-MA (~ 0.5mm) On-line monitoring of interfacial reaction by ATR-FTIR a b

14. /Faculty of Chemical Engineering & Chemistry 14 Instrumental set-up d=1~2 µm 400nm

15. /Faculty of Chemical Engineering & Chemistry 15 Results 120 o C 190 o C 5.4 wt% oxazoline 400nm SAN-oxa layer Ester Oxazoline Amide I Amide II

16. /Faculty of Chemical Engineering & Chemistry 16 Difference Spectroscopy Ester Amide I Oxazoline

17. /Faculty of Chemical Engineering & Chemistry 17 Intensity Vs. Time

18. /Faculty of Chemical Engineering & Chemistry 18 Mirror image overlapping original After reversal

19. /Faculty of Chemical Engineering & Chemistry 19 Effect of temperatures Equilibrium ? Diffusion limitation ?

20. /Faculty of Chemical Engineering & Chemistry 20 Step annealing І : 190 o C ~170 o C Equilibrium ?

21. /Faculty of Chemical Engineering & Chemistry 21 Step annealing II : 150 o C/160 o C/170 o C ~ 190 o C

22. /Faculty of Chemical Engineering & Chemistry 22 Step annealing II : Slope Slope in curve of 190 o C 150 o C ~ 190 o C0.00707 0.00679 160 o C ~ 190 o C0.00329 0.00405 170 o C ~ 190 o C0.00148 0.00141 150 o C/160 o C/170 o C ~ 190 o C

23. /Faculty of Chemical Engineering & Chemistry 23 Effect of content of oxazoline Temp. =190 o C 3.45/1.95.4/1.9 ratio of oxazoline's content 1.8157892.842105 ratio of amide I's intensity 1.9740672.91471

24. /Faculty of Chemical Engineering & Chemistry 24 Effect of thickness of SAN-oxazoline layer Temp. =190 o C

25. /Faculty of Chemical Engineering & Chemistry 25 Solution mixture of SAN and SAN-oxa Temp. =190 o C

26. /Faculty of Chemical Engineering & Chemistry 26 Conclusions  ATR-FTIR can be used to monitor the interfacial reaction between oxazoline and acid groups and follow the kinetics.  There is no side reaction in the system.  It’s not an equilibrium reaction.  low temperature – higher diffusion limitation and vice versa.  The thickness of SAN-oxa layer and the position of the oxazoline group in SAN is not important for the reaction.

27. /Faculty of Chemical Engineering & Chemistry 27 Future Work  A TR-FTIR: do quantitative analysis on the data  E E llipsometry: follow the interlayer formation  T he ellipsometry data will be correlated with the infrared data  O ff-line investigation of the stretching process by FTIR

28. /Faculty of Chemical Engineering & Chemistry 28 Acknowledgement  Otto van Asselen, TU/e  Edgar Karssenberg, TU/e  Martin van Duin, DSM Research, Geleen, The Netherlands  Gert de Wit, GE Advanced Materials, Bergen op Zoom, The Netherlands  Colleagues in the faculty of Chemical Engineering & Chemistry of TU/e

29. /Faculty of Chemical Engineering & Chemistry 29 Thanks for your attention !

30. /Faculty of Chemical Engineering & Chemistry 30

31. /Faculty of Chemical Engineering & Chemistry 31 Morphology developement viscosity of phases,interfacial properties, blend composition, processing conditions Introduction C. Koning, Prog. Pol. Sci (1998), 707

32. /Faculty of Chemical Engineering & Chemistry 32 Capillary Number ---- Drop deformation

33. /Faculty of Chemical Engineering & Chemistry 33 Why oxazoline?? Macosko et al., Polymer 42 (2001), 8171 P(arom.) < P(aliph.)P’(arom.) < P’(aliph.)

34. /Faculty of Chemical Engineering & Chemistry 34 Ellipsometry  The evolution of interface with time under different temperatures

35. /Faculty of Chemical Engineering & Chemistry 35 Model for Ellipsometry

36. /Faculty of Chemical Engineering & Chemistry 36 Off-line investigation of the stretching process by FTIR

37. /Faculty of Chemical Engineering & Chemistry 37 FTIR Microscopy

38. /Faculty of Chemical Engineering & Chemistry 38 Conversion of oxazoline Which one is better

39. /Faculty of Chemical Engineering & Chemistry 39 5.4% SAN-oxa with catalyst 5.4% without catalyst 190deg 2hrs

40. /Faculty of Chemical Engineering & Chemistry 40 5.4% with 55wt% catalyst (to oxazoline) 190deg 2hrs