Living/Controlled Cationic
Polymerization
Cationic Polymerization
Ki
R-X:
R X + MtXm +
R + MtXm+1- iongeneration R2
R1 R1 initiation R1 C X X: Cl, OH, OMe
kc
+
R + CH2 C R CH2 C+ cationization
R2 R2
R3
regioselective
MtXm: AlCl3, BCl3, TiCl4
R1 R1 R1 R1 (head to tail)
R CH2 +
C + CH2 C
kp
R CH2 C CH2 C+ SnCl4, SbCl5
R2 R2 R2 R2 ZnCl2, ZnI2
propagation CH3
R1 R1 R1 R1 R1
kp CH2 C
R CH2 +
C CH2 C + CH2 C R CH2 C CH2 C+ CH 3
n n+1
R2 R2 R2 R2 R2
CH2 C
R1 R1 R1 R1 R1 R1 CH 3
k tr,M
R CH2 +
C CH2 C + CH2 C R CH2 C CH C + CH3 C+ izobutilén -metil-sztirol
n n
R2 R2 R2 R2 R2 R2
R1 R1 R1 R1 CH2 CH CH2 CH
k tr,I
R CH2 C CH2 C+ + R X R CH2 C CH2 C X + R+ OR
n n
R2 R2 R2 R2 chain-transfer (R=Me, nBu, iBu)
R1 R1 R1 R1
k tr,S
R CH2 C CH2 C+ + S R CH2 C CH C + SH+ vinil-éter sztirol
n n
R2 R2 R2 R2
R CH2
R1 R1
C CH2 C+ + MtXm+1-
kt
R CH2
R1 R1
C CH2 C X + MtXm termination
R CH2 C+ + CH2 C
X
n n
R2 R2 R2 R2
Properties of polymers synthesized by traditional cationic
polymerization:
broad molecular weight distribution (Mw/Mn=2-6)
low control of molecular weight, molecular weight distribution and
functionality
Solution ???
Living/Controlled Cationic Polymerization
The Living Polymerization
Ideal Systems Real Systems
fast initiation (ri >> rp) slow initiation (ri < rp)
linear propagation chain-fransfer
no chain-transfer reverzible termination
no termination
Properties of Living Polymerization
The life-time of the chain-end is relatively
long
ln([M]o/[M])=f(time) linear, starts from the
origin
DPn=[M]o/[I]o
Mw/Mn=1+1/DPn
ki
I I+ Initiation
kp
I+ + M IM+
kp
IM+ + M IM2+
kp
IM2+ + M IM3+ Propagation
kp
IMn+ + M IMn+1+
ri >> rp
-d[M]/dt = kp([I+] + [IM+] + [IM2+] +…..+ [IMn+])[M]
[I]o
1. ln([M]o/[M]) = kp[I]ot
2. DPn = C[M]o/[I]o
Poisson-distribution
Degree of Polymerization
2
ideal
termination (kp/kt=100 M-1)
slow initiation (kp/ki=100 M-1)
1.5
[M]o=1 M
[I]o=0,01 M
kp=1M-1s-1
ln([M]o/[M])
0.5
0
0 50 100 150 200
idő (s)
100
[M]o=1 M
90 Mw/Mn=1,20
[I]o=0,01 M
Mw/Mn=1,25
80 Mw/Mn=1,01
70
60
Mw/Mn=1,50
DPn 50
40 M /M =1,30
w n
30
20
ideal
10 Chain-transfer (kp/ktr=100)
slow initiation (kp/ki=100 M-1)
0
0 0.2 0.4 0.6 0.8 1
konverzió
coinitiator
methanol
solvent + initiator (mI) + monomer (mo)
-ln(1-C)
t1 t2 t3 t4 t5
t1 t2 t3 t4 t5
Mn
m1 m2 m3 m4 m5
ln([Mo]/[M])=-ln(1-C) slope=1/nI
C=mp/mo
mp=mass of the polymer formed m1 m2 m3 m4 m5
mo=intial mass of the monomer
+ Controlling cationic polymerization
(„removing” of protic impurities)
"H 2O" + BCl3 H+ + BCl3OH- H
+nM H H
H
H H
HMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMM+
H
H
N H
H H
H
H H
H
proton “trap”
H H
H H
H
H H
2,6-di-tbuthyl-pyridin
Cl
Cl
Cl
Initiators and addtives applied in the polymerization of isobutylene
Initiators: Without additives:
cumyl-alcoholes/BCl3
CH3 CH3 CH3 cumyl-esters/BCl3
C X X C C X cumyl-ethers/BCl3
CH3 CH3 CH3 cumyl-esters/TiCl4
X: Cl, OH, OCH3, OCOCH3
kumil-származékok
Cumyl-derivatives In the presence of
nucleophiles:
CH3 CH3
cumyl-alcoholes/Nu/TiCl4
CH3 CH CH2 C Cl
cumyl-chloride/Nu/TiCl4
CH3 CH3
2,4,4-trimetil-2-klór-pentán
2-chloro-2,4,4-trimethylpentane
cumyl-ethers/Nu/TiCl4
(TMPCl)
(TMPCl) cumyl-esters/Nu/BCl3
TMPCl/Nu/TiCl4
Nu: DMSO, THF, DOP
In the presence of salts:
cumyl-chloride/nBu4NCl/TiCl4
cumyl-chloride/nBu4NCl/BCl3
Application of Living Polymerization ???
Macromolecular Engineering
Goal: Synthesis of macromolecules with special chemical,
biological and physical properties
CH3
Initiator: C Cl Coinitiator: TiCl4
CH3
CH3 CH3
C - Ti2Cl9- CH2 C
CH3 CH3
CH2 CH O CH3 - Ti2Clx(OR)9-x-
TiCl4 > TiCl3(OR) > TiCl2(OR)2 > TiCl(OR)3 > Ti(OR)4
Ti(OR)4 ()
2. monomer
+ +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- +- -
DPn,PIB = 15 = [M]o,IB/[I]o DPn,PMVE = 10 = [M]o,MVE/[I]o
Linear block copolymer with controlled segment lengths (AB-type)
