Atrp Polymerization
Páginas: 7 (1556 palabras)
Publicado: 31 de mayo de 2012
AGET ARGET ATRP for block copolymers synthesis
Sebastien Viale Summer 2008
Outline
• Mechanism of ATRP, AGET, ARGET • Synthesis of Block copolymers with AGET ARGET ATRP • Apply these techniques on the synthesis of AB and ABA block copolymers using PEG derivatives as macroinitiators:
– AB with mPEG and Styrene and MMA – ABA with PEG with Styrene and MMA
• Synthesis of on-demandhydrophilic monomers and study of the chain extension by AGET • mPEG/PEG chain extension with Styrene under ARGET
History of ATRP
• 1995 two main papers from Matyjaszewski and Sawamoto • Sawamoto with Ruthenium
• Matyjaszewski with Copper
Controlled/"Living" Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition Metal Complexes" J. S. Wang, K. Matyjaszewski,J. Am. Chem. Soc., 117, 5614 (1995)
ATRP
NPPMI (R = n-C3H7) N NOPMI (R = n-C8H17) (5.0x10-10) R N
Effect of Ligand Structures on KATRP
CuI/L with EBiB, MeCN, r.t
N N
N N
-8
N
N N bpy (3.9x10-9)
N
N
-8
dNbpy (3.0x10 )
N N N
N
N
-8
N N N
N N N
N N
N N
PMDETA (7.5x10 )
N[2,2,2] (1.1x10 )
BPMPA (6.2x10-8)
TPEDA (2x10-6)
BPED (1.1x10-5)Active
10
-9
10
-8
10
-7
10
-6
10
N
-5
10
N N N N
-4
10
-3
N
KATRP
N N N N
N
N
N N
N N
N
N
N
N
-10
N[2,2,3] (1.5x10-7)
N[3,2,3] (3.2x10-9)
)
TPMA (1.0x10-5)
CN
O O N N N O O O O N O But O O O
N[2,3,2] (4.2x10
CN NC N N N
Cyclam-B (2.0x10-3)
tBu O O N N N O But O
tBu O O
N
N O O O tBu O tBuN N N N
O
CN
O
N N N
N NC CN
-9
O O
Et6TREN (9.4x10
-10
)
AN6TREN (1.7x10 )
Me6TREN (1.5x10-4)
MA6TREN (1.7x10-8)
BA6TREN (5.2x10-8)
Effect of Initiator Structures on KATRP
CuI/TPMA, MeCN, r.t
Cl
Br
Cl
O O Cl
Br
O
O O
O
O Br MBriB (1.8x10-5)
Br
O
BzCl (4.5x10 -7 )
BzBr (6.8x10-7)
PECl (8.6x10-7)
EtCliB (1.5x10-6)PEBr (4.6x10-6)
Br EtBriB (1.0x10-5)
EBPA (1.0x10-3)
Active
10
-7
10
O
-6
10 O
O
-5
10
-4
Cl
KATRP
Br
10
-3
O O I MIP (2.2x10-8)
O O Cl MClP (3.8x10-8)
O Br tBBrP (4.2x10-8)
O
O Br
O O
MClAc (4.2x10 -7 )
Cl CN
Cl
CN
MBrAc (3.2x10-7)
Br MBrP (3.2x10-7)
ClPN (2.2x10-5)
ClAN (3.1x10 -5 )
Br
CN
CN
BrAN(5.6x10-5)
BrPN (1.1x10-4)
AGET
Cu (II) less sensitive to air and reduce in-situ [Reducing agent] >>>[Cu]
AB structure with AGET approach
Synthesis of PEG/mPEG macroinitiator
AB structure
O OH O O Br Br
+
Br O
n
n
St/mPEG/CuBr2/dNoniBP/TIN: 100/1/1/2/0.45
1.8 1.6 1.4 1.2 Ln [M0/Mt] 1 1.25 0.8 1.2 0.6 0.4 0.2 0 0 1 2 3 4 5 6 Time in hours 1.15 1.1 1.05 1 1.51.45 1.4 1.35 1.3 PDI
16000 14000 12000 Mn in g.mol-1 10000 8000 6000 4000 2000 0 0 20 40 60 80 100 Monomer conversion
8H 7H 6H 5H 4H 3H 2H 1H 0H
1000
10000
100000
St/mPEG/CuBr2/PMDETA/TIN: 100/1/1/1/0.45
2.5 2 1.8 2 1.6 1.4 1.5 1.2 1 1 PDI
Ln [M0/Mt]
0.8 0.6
0.5
0.4 0.2
0 0 0.66 1 1.5 1.66 2 3 4 5 6 7 8 Time in hours
0
30000
25000
20000 Mn ing.mol-1
15000
10000
5000
0 0 20 40 60 80 100 Monomer conversion
9 8 7 6 5 4 3 2 1 0
H H H H H H H H H H
1000
10000
100000
1000000
MMA/mPEG/CuBr2/dNoniBP/TIN: 100/1/1/2/0.45
0.6 2 1.9 0.5 1.8 1.7 1.6 0.3 1.5 1.4 0.2 1.3 1.2 1.1 0 0 1 2 4 5 6 7 8 Time in hours 1 PDI
0.4 Ln [M0/Mt]
0.1
9000 8000 7000 6000 Mn in g.mol-1 5000 4000 3000 2000 1000 0 0 5 10 15 20 2530 35 Monomer conversion
Remaining macroinitiator
8H 6H 5H 4H 3H 2H 1H 0H
1000
10000
100000
ABA structure
ABA structure
O HO O OH
Br
+
Br
n
Br O O Br O O
n
St/PEG/CuBr2/dNonyBIPY/TIN: 100/1/1/2/0.45
3.5 3 1.8 2.5 Ln [M0/Mt] 2 1.5 1 0.5 1.1 0 0 1 2 3 4 5 6 7 8 Time in hours 1 1.7 1.6 1.5 1.4 1.3 1.2 PDI 2 1.9
16000 14000 12000 10000 8000 6000 4000...
Sebastien Viale Summer 2008
Outline
• Mechanism of ATRP, AGET, ARGET • Synthesis of Block copolymers with AGET ARGET ATRP • Apply these techniques on the synthesis of AB and ABA block copolymers using PEG derivatives as macroinitiators:
– AB with mPEG and Styrene and MMA – ABA with PEG with Styrene and MMA
• Synthesis of on-demandhydrophilic monomers and study of the chain extension by AGET • mPEG/PEG chain extension with Styrene under ARGET
History of ATRP
• 1995 two main papers from Matyjaszewski and Sawamoto • Sawamoto with Ruthenium
• Matyjaszewski with Copper
Controlled/"Living" Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition Metal Complexes" J. S. Wang, K. Matyjaszewski,J. Am. Chem. Soc., 117, 5614 (1995)
ATRP
NPPMI (R = n-C3H7) N NOPMI (R = n-C8H17) (5.0x10-10) R N
Effect of Ligand Structures on KATRP
CuI/L with EBiB, MeCN, r.t
N N
N N
-8
N
N N bpy (3.9x10-9)
N
N
-8
dNbpy (3.0x10 )
N N N
N
N
-8
N N N
N N N
N N
N N
PMDETA (7.5x10 )
N[2,2,2] (1.1x10 )
BPMPA (6.2x10-8)
TPEDA (2x10-6)
BPED (1.1x10-5)Active
10
-9
10
-8
10
-7
10
-6
10
N
-5
10
N N N N
-4
10
-3
N
KATRP
N N N N
N
N
N N
N N
N
N
N
N
-10
N[2,2,3] (1.5x10-7)
N[3,2,3] (3.2x10-9)
)
TPMA (1.0x10-5)
CN
O O N N N O O O O N O But O O O
N[2,3,2] (4.2x10
CN NC N N N
Cyclam-B (2.0x10-3)
tBu O O N N N O But O
tBu O O
N
N O O O tBu O tBuN N N N
O
CN
O
N N N
N NC CN
-9
O O
Et6TREN (9.4x10
-10
)
AN6TREN (1.7x10 )
Me6TREN (1.5x10-4)
MA6TREN (1.7x10-8)
BA6TREN (5.2x10-8)
Effect of Initiator Structures on KATRP
CuI/TPMA, MeCN, r.t
Cl
Br
Cl
O O Cl
Br
O
O O
O
O Br MBriB (1.8x10-5)
Br
O
BzCl (4.5x10 -7 )
BzBr (6.8x10-7)
PECl (8.6x10-7)
EtCliB (1.5x10-6)PEBr (4.6x10-6)
Br EtBriB (1.0x10-5)
EBPA (1.0x10-3)
Active
10
-7
10
O
-6
10 O
O
-5
10
-4
Cl
KATRP
Br
10
-3
O O I MIP (2.2x10-8)
O O Cl MClP (3.8x10-8)
O Br tBBrP (4.2x10-8)
O
O Br
O O
MClAc (4.2x10 -7 )
Cl CN
Cl
CN
MBrAc (3.2x10-7)
Br MBrP (3.2x10-7)
ClPN (2.2x10-5)
ClAN (3.1x10 -5 )
Br
CN
CN
BrAN(5.6x10-5)
BrPN (1.1x10-4)
AGET
Cu (II) less sensitive to air and reduce in-situ [Reducing agent] >>>[Cu]
AB structure with AGET approach
Synthesis of PEG/mPEG macroinitiator
AB structure
O OH O O Br Br
+
Br O
n
n
St/mPEG/CuBr2/dNoniBP/TIN: 100/1/1/2/0.45
1.8 1.6 1.4 1.2 Ln [M0/Mt] 1 1.25 0.8 1.2 0.6 0.4 0.2 0 0 1 2 3 4 5 6 Time in hours 1.15 1.1 1.05 1 1.51.45 1.4 1.35 1.3 PDI
16000 14000 12000 Mn in g.mol-1 10000 8000 6000 4000 2000 0 0 20 40 60 80 100 Monomer conversion
8H 7H 6H 5H 4H 3H 2H 1H 0H
1000
10000
100000
St/mPEG/CuBr2/PMDETA/TIN: 100/1/1/1/0.45
2.5 2 1.8 2 1.6 1.4 1.5 1.2 1 1 PDI
Ln [M0/Mt]
0.8 0.6
0.5
0.4 0.2
0 0 0.66 1 1.5 1.66 2 3 4 5 6 7 8 Time in hours
0
30000
25000
20000 Mn ing.mol-1
15000
10000
5000
0 0 20 40 60 80 100 Monomer conversion
9 8 7 6 5 4 3 2 1 0
H H H H H H H H H H
1000
10000
100000
1000000
MMA/mPEG/CuBr2/dNoniBP/TIN: 100/1/1/2/0.45
0.6 2 1.9 0.5 1.8 1.7 1.6 0.3 1.5 1.4 0.2 1.3 1.2 1.1 0 0 1 2 4 5 6 7 8 Time in hours 1 PDI
0.4 Ln [M0/Mt]
0.1
9000 8000 7000 6000 Mn in g.mol-1 5000 4000 3000 2000 1000 0 0 5 10 15 20 2530 35 Monomer conversion
Remaining macroinitiator
8H 6H 5H 4H 3H 2H 1H 0H
1000
10000
100000
ABA structure
ABA structure
O HO O OH
Br
+
Br
n
Br O O Br O O
n
St/PEG/CuBr2/dNonyBIPY/TIN: 100/1/1/2/0.45
3.5 3 1.8 2.5 Ln [M0/Mt] 2 1.5 1 0.5 1.1 0 0 1 2 3 4 5 6 7 8 Time in hours 1 1.7 1.6 1.5 1.4 1.3 1.2 PDI 2 1.9
16000 14000 12000 10000 8000 6000 4000...
Leer documento completo
Regístrate para leer el documento completo.