an introduction about cyclic olefin polymerization

2. Exhibitor:
Ahmad
Soleymannezhad
Najafabadi
Guidance Masters:
Dr. Ahmadjo
Dr. Mortazavi
Summer
2016

3.  Introduction
 Mechanism of cycloolefin homopolymerization
Review on prior studies
Conclusion

4. 4
Poly olefins
Poly olefins are large group of polymers that due to their favorable
mechanical and physical properties have wide applications.
Poly olefins include:
Poly ethylene
Poly propylene
poly 1-hexane
poly 1-butane
and etc.

5. cyclobutene
cyclopentene
bicyclic olefins
reasons of major emphasis on norbornene polymers:
 can be (co-)polymerized by a variety of polymerization pathways
 represent a wide variety of monomers and hence polymers and
application areas
5
norbornene
(C7H10)

6. 6
Mechanisms
Ring Opening
Metathesis Polymerization(ROMP)
Addition or vinyl polymerization
Cationic or radical Polymerization

7. 7
 first was described in 1960 by DuPont
 double bonds in the polymer backbone
can be crosslinked
 single-site catalytic systems
metal halides:
Alkylating agents:
promoting agents:
Tungsten
Molybdenum
Rhenium
Ruthenium
R4Sn, Et2AlCl
O2, EtOH, PhOH

8. 8
 First was described in 1967
 The cationic polymerization was started with EtAlCl2
 The result is a low molar mass oligomeric material
( Mn = 21400 g/mol)
54 % conversion, Mw/Mn = 1.07
at 100 % conversion; Mw/Mn = 1.34

9. 9
homopolymerization
1. early transition metals, especially the metallocene catalysts of zirconium
2. late transition-metal palladium(II) and nickel(II) catalysts
3. central transition metals chromium and cobalt
catalyst
 high thermal stability
 low moisture absorption
 high optical transparency
 high glass transition temperature
 deep ultraviolet photoresistors
 cover layer for liquid crystal displays
 packaging and gas separation
properties
applications

10. 10
 copolymerization of cyclic olefins with ethylene or α-olefins (COC’s)
 metallocene and half-sandwich/MAO-catalysts
copolymerization
 low shrinkage
 barrier resistance
 good optical properties
 Broad range of glass transition temperature(65-180)
properties
applications
 Optics
 Packaging
 Capacitors
 Medical equipment
 Binder in printer toner
 Digital data storage devices (CD-ROM)

11. 11
 Central metal of catalyst
 Ligand of complexes
 Al/Ni molar ratio
 Type of co-catalyst
 Polymerization conditions(solvent, temperature, chain transfer agent)

12. 12
Scheme of catalyst complexes

13. 13
Table 1. norbornene polymerization in toluene. 15g norbornene, 3µmol
catalyst, 2.66mmol MAO, in 50ml toluene for 120h at 500C.
Scheme1. catalyst complexes

14. 14
Table 2. norbornene polymerization in toluene. 15g norbornene, 3µmol
catalyst, 2.66mmol MAO, in 50ml toluene for 120h.
Scheme3. catalyst complexes

15. 15
Table 3. norbornene polymerization in toluene. 15g norbornene, 3µmol
catalyst, 2.66mmol MAO, in 50ml toluene for 120h, at 500C.
(ODCB: ortho-dichlorobenzene)
Scheme4. catalyst complexes
Toluene, ODCB

16. Table 4. norbornene polymerization in toluene. 15g norbornene, 3µmol
catalyst A-I/Ni, 2.66mmol MAO, in 50ml toluene for 120h, at 500C.
16

17. 17

18. Table 1. norbornene polymerization in toluene,
0.0425mol norbornene, 5µmol catalyst Ni
for 30min, at 500C.
18

19. Table 2. norbornene polymerization in toluene,
0.0425mol norbornene, 5µmol catalyst Ni,
[Al]/[Ni]=600, for 30min.
19

20. 20
Activity of catalyst: 1>2>4>5>6>3
catalysts ligand bulky: 5>6>3>2>1>4

21. Figure 1. FTIR spectrum of polynorbornene obtained by
5/MAO under 50 0C
21

22. Figure 2. H-NMR spectrum of polynorbornene in
o-C6H4Cl2 and o-C6D4Cl2 at 120 0C
obtained by 1/MAO under 50 0C
22

23. Figure 2. TG/DTG curve of polynorbornene obtained
by 5/MAO under 50 0C
23
R1: Me
R2: Me
R3: 2,6-diisopropylph

24. Nickel salen complex
24

25. Table 1. norbornene polymerization. 0.215mmol norbornene, catalyst Ni
salen/MAO, at 250C. MAO-I: Me/Al =1.37 ; MAO-II: Me/Al =1.16
25

26.  Norbornene can be polymerized with three mechanisms (ROMP,
cationic, addition polymerization )
 Polymers produced with addition polymerization are saturated
polymers with good physical and mechanical properties
 Parameters influence on Addition polymerization are: central metal of
catalyst, ligand of complexes, ratio of co-catalyst to catalyst,
polymerization conditions,…
 Ni based catalysts are more active than other metals
 Increasing the ratio of co-catalyst to catalyst leads to activity and
molecular weight increment
 Increasing the temperature leads to activity increment but the
molecular weight reduction
26

27. [1] B. Rieger, L. S. Baugh, S. Kacker, and S. S. Eds, Late Transition Metal Polymerization
Catalysis. wiley vch, 2003.
[2] C. Janiak and P. G. Lassahn, “Metal catalysts for the vinyl polymerization of
norbornene,” Mol. Catal., vol. 166, pp. 193–209, 2001.
[3] G. Scalcione and P. D. I. Milano, “Tesi di Dottorato di GIULIA SCALCIONE Matricola
784957 POLITECNICO DI MILANO,” no. Cii, 2014.
[4] M. Licchelli, “Vinylic Polymerization of Norbornene by Late Transition Metal-Based
Catalysis,” Macromol. Chem. Phys., no. i, pp. 2052–2058, 2001.
[5] X. He and Q. Wu, “Polymerization of Norbornene Using Bis (β-ketoamino ) nickel (
II )/ MAO Catalytic Systems,” Appl. Polym. sience, pp. 45–47, 2005.
[6] S. Borkar and P. K. Saxena, “Nickel ( salen ) / methylaluminoxane catalyzed
polymerization of norbornene,” Polym. Bull., vol. 172, pp. 167–172, 2000.
[7] X. Li and Y. Li, “Vinylic Polymerization of Norbornene by Neutral Nickel ( II ) -Based
Catalysts,” Polym. Chem., no. Ii, pp. 2680–2685, 2002.

28. Thank you
Any question?