The document summarizes various mechanisms of polymerization, including chain-growth polymerization, step-growth polymerization, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, Ziegler-Natta catalysis, ring-opening polymerization, and the polymerization of cyclic ethers, cyclic amides, and siloxanes. It discusses reaction initiation, mechanisms, applications, and stereochemistry for different polymerization methods.

1. AMITY UNIVERSITY
RAJASTHAN
Mechanism
of Polymerization
Present By
Subhrangsu Sekhar Dey
M.Sc Applied Chemistry

2. Introduction
Monomers has to be two functionality for
polymerization.

3. Reaction Mechanism
1.Addition or Chain growth
1.1.Radical polymerization
1.2.Cationic polymerization
1.3.Anionic polymerization
2.Condensation or Step growth

4. Chain-growth Polymerization

5. Step-growth polymerization

6. Step Growth V/S Chain Growth

7. Application

8. Thermodynamics of Polymerization

9. Polymerizability of Monomers

10. Active Intermediates

11. Substituent Effects V/s Initiator

12. Free Radical Polymerization

13. Branching of the Polymer Chain

14. Application

15. Cationic Polymerization
the alkene monomer
reacts with an electrophile

17. Application

18. Anionic Polymerization
Nonterminated chains are called living polymers
The chains remain active until they are killed

19. Application

20. Co-ordination Polymerization
Ziegler–Natta catalyst
Polymerization of Dienes

21. Mechanism Of
Ziegler Natta Catalysis

22. Ziegler–Natta catalyst
Synthesis of Synthetic Rubber

23. Ring-Opening Polymerization

25. Stereochemistry of
Polymerization
substituents on the same side
substituents regularly alternate on both sides

26. General Mechanism of Chain-
Growth Polymerization

27. Progress of a Step-Growth
Polymerization

28. Step Growth Polymerization
Nylon 6,6

29. Cyclic Ethers
tertrahydropyran
dioxane
polymerization
unreactive
difficult
(substituents usually will prevent it)

30. Cyclic Ethers
1) Ethylene Oxide
RO
(DMSO)
PEO
Living Polymerization

31. Cyclic Ethers
Thermo Plastic Elastomer
3,3-bis(azidomethyl)oxetane (BAMO)
O
CH2
CH2 N3
N3
O CH2 C
CH2N3
CH2N3
CH2
3-azidomethyl-3-methyl oxetane (AMMO)
O
CH3
CH2 N3
O CH2 C
CH2N3
CH3
CH2
BAMO AMMO BAMO

32. Cationic Polymerization
of Cyclic Ethers
OF3C S
O
O
O S CF3
O
O
O
F3C S
O
O
O S CF3
O
O
Difunctional PTMO (initiated by triflic anhydride)
O CH2CH2CH2CH2OF3C S
O
O
S
O
O
CF3

33. Cyclic Amides
C
N O
H
n
CH2
CH2 CH2 N CCH2CH2 CH2
H
O n
CH2 CH2 CCH2CH2 CH2N
O
N
O
H
Na
CH2
CH2
C
N
H2C
H2C
H2C
O
H
CH2 CH2 CCH2CH2 CH2N
O
N
O
H
H
CH2
CH2
C
N
H2C
H2C
H2C
O
+
imide dimer: actural initiating species:
exo-carbonyl makes it more reactive!Na
CH2
CH2
C
N
H2C
H2C
H2C
O
H
CH2
CH2
C
N
H2C
H2C
H2C
O
H
CH2
CH2
C
N
H2C
H2C
H2C
O
NaH
Anionic Initiated Polymerization

34. Siloxanes may be cyclic, linear or cross linked
polymer
Cyclosiloxanes

35. Mechanism of Siloxanes

37. Ring opening Siloxane
Siloxanes Polymerization