polymer mechanism

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AMITY UNIVERSITY RAJASTHAN

Mechanism of Polymerization

Present BySubhrangsu Sekhar Dey

M.Sc Applied Chemistry

Introduction

Monomers has to be two functionality for polymerization.

Reaction Mechanism

1.Addition or Chain growth

1.1.Radical polymerization

1.2.Cationic polymerization

1.3.Anionic polymerization

2.Condensation or Step growth

Chain-growth Polymerization

Step-growth polymerization

Step Growth V/S Chain Growth

Application

Thermodynamics of Polymerization

Polymerizability of Monomers

Active Intermediates

Substituent Effects V/s Initiator

Free Radical Polymerization

Branching of the Polymer Chain

Application

Cationic Polymerization

the alkene monomerreacts with an electrophile

Application

Anionic Polymerization

Nonterminated chains are called living polymers

The chains remain active until they are killed

Application

Co-ordination Polymerization Ziegler–Natta catalyst

Polymerization of Dienes

Mechanism Of Ziegler Natta Catalysis

Ziegler–Natta catalyst Synthesis of Synthetic Rubber

Ring-Opening Polymerization

Stereochemistry of Polymerization

substituents on the same side

substituents regularly alternate on both sides

General Mechanism of Chain- Growth Polymerization

Progress of a Step-Growth Polymerization

Step Growth Polymerization

Nylon 6,6

Cyclic Ethers

O

O

O

O OO

tertrahydropyrandioxane

polymerization

unreactive

difficult(substituents usually will prevent it)

Cyclic Ethers

A MO

A CH2 CH2 O M

OBuLi

1) Ethylene Oxide

RO

(DMSO)

PEO

Living Polymerization

SCH3

O

H3C

A = HO

R

Cyclic EthersThermo 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

Cationic Polymerizationof 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

Cyclic AmidesC

N O

H

nCH2

CH2 CH2 N CCH2CH2 CH2

H

O n

CH2 CH2 CCH2CH2 CH2N

O

N

O

H

Na

CH2

CH2

CN

H2C

H2C

H2C

OH

CH2 CH2 CCH2CH2 CH2N

O

N

O

H

H

CH2

CH2

CN

H2C

H2C

H2C

O

+imide dimer: actural initiating species:exo-carbonyl makes it more reactive!Na

CH2

CH2

CN

H2C

H2C

H2C

OH

CH2

CH2

CN

H2C

H2C

H2C

OH

CH2

CH2

CN

H2C

H2C

H2C

O

NaH

Anionic Initiated Polymerization

Siloxanes may be cyclic, linear or cross linked polymer

Cyclosiloxanes

Mechanism of Siloxanes

Ring opening Siloxane

Siloxanes Polymerization

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