Summary of my research work ( industrial projects are not presented on these slides)

1. Synthesis of Branched, Cyclic & Functional Polymers Vijay Chavan, Dr. Roderic P. Quirk Department of Polymer Science, The University of Akron, Akron, Ohio- 44325

2. Department of Polymer Science at Akron Program Since 1967 First College of Polymer Science & Engineering in the world New Building constructed in 1991

4. 1) Controlled synthesis of Star Branched Polymers Vijay Chavan, Roderic P. Quirk, Manuela Ocampo

8. 1) Star PS using DVB Degree of Branching from 5 to 39 f = Mn branch /Mn linear = 5-39 [DVB]/[PSLi] = 2 to 30 Hseih, H.L.; Quirk, R.P. Anionic Polymerization: Principles and Practical Appplications ; Marcel Dekker, Inc.: New York, 1996 Possibility of gelling

9. 2) Star polymers by condensing living P - Li + with chlorosilanes Morton, M.; Helminiak, T. E.; Gadkary, S. D.; Bueche, F. J. Polym. Sci. 1962 , 57 , 471-482 Mn star / Mn arm = 4.09 After fractionation PDI= 1.09

10. Combination of vinyl and chlorine group Nucleophilic substitution PS - Li + VDMCS VInyldimethylchlorosilane +

11. Chaumont, P.; Herz, J.; Rempp, P. Eur. Polym. J. 1979 , 15 , 537-540. THF, -70 0 C Excess Mn = 20k PDI = 1.1 Addition of living PSLi to VDMCS Reaction done in THF at -70 0 C

12. Reaction of PSLi with VDMCS Branches upon branches Wilczek, L., US Patent 6,740,723 , Feb 11, 2003 f max = Mn branched / Mn linear = 5 THF , -78 0 C Approx 1:1 ratio Dupont

14. Experiment Styrene Methanol VDMCS Methanol Ampoule for base sample Vacuum Methanol Solution Ampoule for base sample after 12 hrs Inlet for initiator

15. GPC Analysis M n base= 2,500 g/mol PDI = 1.02 M n : 23,000 g/mol PDI: 1.3

16. 1 H NMR No Vinyl peaks

17. -37.30 0 TMS PS-VDMCS-1.5-30C-3day Reported peaks for –Si-Cl (17.65 ppm) and –Si-OCH 3 (6.66 ppm) are absent indicating complete substitution of Cl 29 Si NMR

18. PS-VDMCS-1.5-50C-3day PS-VDMCS-2.5-30C-3day PS-VDMCS-2.5-50C-3day PS-VDMCS-5-30C-3day PS-VDMCS-5-50C-3day

19. Effect of concentration of VDMCS Behavior unlike DVB

21. Viscosity of Star and Linear g η [ η ] star [ η ] linear = Contraction parameter

22. Contraction factor g η = [ η ] branched / [ η ] linear Deffieux, A.; Schappacher, M. Macromolecules , 1999 , 32, 1797-1802 *Roovers, J. Branched Polymers II , Springer, 1999 , 169 (f = Mn star / Mn linear ) gη literature For f=8.9 is 0.44* Observed is 0.46

23. Contraction parameter observed vs theoretical 0.46 0.47 8.33 0.47 0.53 7.94 0.49 0.49 7.50 0.42 0.40 9.36 0.47 0.48 8.09 0.44 0.46 8.90 Calculated g n Observed [n]/[n]lin f

24. Melt Viscosity Data Linear Mn = 18k, PDI= 1.02 Star 17k, PDI = 1.21, Star 22k , PDI = 1.30 Constant strain Cone and plate rheometer Newtonian region

25. VDMCS star , Mn = 23k , PDI = 1.47 DVB Star , Mn = 26k , PDI = 1.58 Thermal Stability

26. Star Polystyrene

28. Vijay Chavan*, Roderic P. Quirk, Shih Fan Wang, Mark D. Foster, Rebecca Agapov, Rahul Kulkarni, Xinfei Yu, Wumin Yu Topographical Evidence of Cyclic Polymers

29. Cyclic Polymer

32. A)Cyclization by anionic polymerization mg of product in liters of solvent Mixtures of products Geiser, D.; Hocker, H. Macromolecules 1980 , 13 , 653. Slow addition Tetrahydropyran Mn = 4k-24 k, Smart way of separation Reacted the linear polymers with High MW PSLi and fractionated

33. B)Cyclization by click chemistry Laurent, B.A.; Grayson, S.M. J. Am. Chem. Soc. , 2006, 128 (13), 4238 75 o C, CuBr,PMDETA, ATRP Mn = 2k, PDI = 1.08 200 mg product for 1 liter solvent

34. 2) Ring opening metathesis by Dr. Robert Grubbs Nobel Prize Winner in Chemistry 2005 http://en.wikipedia.org/wiki/File:Robert_Grubbs.jpg Can cyclic catalyst make cyclic polymer ? Fürstner, A.; Ackermann, L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001 , 7, 3236.

35. Polymer catalyst http://upload.wikimedia.org/wikipedia/commons/0/0e/Making_soapbubbles-SteveEF.jpg

36. Ru Complex A F ürstner, A.; Ackermann , L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001 , 7, 3236. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002 , 297 , 2041-2044. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. J. Am. Chem. Soc. 2003 ,125 , 8424-8425. Complex A

37. Cyclic catalyst F ürstner, A.; Ackermann , L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001 , 7, 3236. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002 , 297 , 2041-2044. Bielawski, C. W.; Benitez, D.; Grubbs, R. H. J. Am. Chem. Soc. 2003 ,125 , 8424-8425. Red Yellow

38. Complex 12c F ürstner, A.; Ackermann , L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001 , 7, 3236. Pentane/Ether : 4:1 volume ratio Argon Argon

39. 31 P NMR linear catalyst

40. 31 P NMR Cyclic catalyst

41. Synthesis of Cyclic Polybutadiene Mn = 88 k, PDI = 2.06 CDT conc. 2.92 mol/L 5 g cyclic polymer in 10 mL solution 80% yield

42. Log M n vs elution time

43. Intrinsic viscosity vs Log M n of linear (broad polydispersity index PDI) and cyclic polybutadiene

44. SEC chromatogram of cyclic polybutadiene and linear polybutadiene (narrow PDI prepared by anionic polymerization)

47. Synthesis of cyclic polymer brush Schappacher, M.; Deffieux, A. Science 2008 , 319 , 1512-1515

48. AFM images

49. Example of grafting on 1,4-polybutadiene Hydrosilation on backbone Iraqi, A.; Seth, S.; Vincent, C. A.; Cole-Hamilton, D.; Watkinson, M. D.; Graham, I. M.; Jeffrey, D. Journal of Materials Chemistry 1992 , 2 , 1057-1064.

50. Polybutadiene composition 1,4-polybutadiene units

51. Results of hydrosilation

52. Grafting of CyPBD with PS-SiH 0.24 mmols

53. SEC chromatograms of cylic polybutadiene, starting PS-SiH and grafted polymer.

54. Table 1 Molecular weight data of starting and grafted polymers 6.19 12,410,000 2,004,000 Grafted Ring 3 2.06 182,600 88,400 CyPBD 2 1.01 8,300 8,300 PS-SiH 1 M w /M n M w (g/mol) M n (g/mol) Sample ID Sr.No

55. AFM imgaes Calculated: 61k Inner diameter: 70-80 nm Outer diameter: 160-190 nm Height: ~ 4 Ǻ

57. Preference for reduction over electrophilic addition by polyisobutylene cations Vijay Chavan, Prof Roderic P.Quirk, Prof. Judit E. Puskas

58. Cationic Stability Carey, F. A.; Tremper, H. S. J. Org. Chem. 1971 , 36 , 758-761.

59. Reaction scheme Hexanes: MeCl 60 : 40 [DtBP]= 0.007 mol/L; [TMPCl] = 0.035 mol/L; [IB] = 0.577 mol/L; [VPDS]= 0.047 mol/L; [TiCl4]= 0.227 mol/L; [DMA]= 0.019 mol/L

60. Figure 1: GPC trace of PIB-Cl and Part 2 a) Refractive Index (RI) detector response b) Light scattering data.

62. Table 1: Molecular weight data [DtBP]= 0.007 mol/L; [TMPCl] = 0.035 mol/L; [IB] = 0.577 mol/L; [VPDS]= 0.047 mol/L; [TiCl4]= 0.227 mol/L; [DMA]= 0.019 mol/L 1.27 2,150 1,700 1,900 1.25 1,950 1,550 PDI Part 2 M w Part 2 (GPC) (g/mol) M n part 2 (GPC) (g/mol) M n Base (NMR) (g/mol) PDI Base M w base (GPC) (g/mol) M n Base (GPC) (g/mol)

63. Figure 2: Proton NMR of PIB-Cl starting polymer

64. Figure 3: Proton NMR of part 2.

65. Figure 4: 13 C NMR of PIB-Cl

66. Figure 5: 13 C NMR of part 2

67. Figure 6 : Mechanism