Nitroxide mediated

polymerization
DR. DIPAK PINJARI
ICT, MUMBAI
Outline

 Introduction
 Type of NMRP Initiators
 Mechanism
 Kinetics
 Application
 Pros & Cons
Introduction

 Nitroxide mediated free radical polymerization (NMRP, NMP) is th

oldest stable free radical polymerization (SFRP) technique.

 allows for the preparation of polymers with narrow molecular ma

distribution, predictable molecular weight and composition, as w
as well-defined polymer architecture and polymers with a variab
functionality.

 NMRP was invented by David Solomon, Paul Cacioli, Glen

Waverley and Ezio Rizzardo in 1986
 Type of NMRP Initiators

. 2,2,6,6-Tetramethyl-1-piperidinyloxy
(TEMPO)

. 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO)

. 2,2,5-trimethyl-4-(isopropyl)-3-azahexane-3-nitroxide (BIPNO)
Mechanism

 living-like polym’n possible due to

 stable nitroxide ~ no self rxn ~ ‘persistent radical’
 weak C-O bond
 small K most chains dormant  very low [M.]
 negligible termination
 equal chance to growth, no AA  low PDI
Developments

 ST polym’n with TEMPO at 125 ºC

 with conventional initiator
 ‘stable-free-radical(-mediated) polym’n (SFRP)’
 ST, acrylates, dienes at lower Temp
 with TIPNO, SGI
 use of monomer-alkoxyamine as initiator
 better control of [M]
 current standard
Kinetics of NMP

 plot linear only in early stage; positive curvature later

 ‘persistent radical effect (PRE)’
 termination [M.] , (relative) [NO.]   termination
Modified kinetics

~ linear

 AA possible, but not critical (kt-1/3)

 MM in NMP

 c ~ (fractional monomer) conversion

 PDI? should be ≈1; actually 1.1 - 1.3
Side reactions in NMP

 serious in MMA ~ NMP not for MMA

yet

 purely thermal (self) initiation of ST (at 80 ºC)

 Practically, compensate ‘persistent radical
effect’
 Application

• Synthesis of electrolyte materials for lithium batteries,

• Organic electronics
• Photolithography,
• Drug delivery systems.
• Development of antimicrobial surfaces.