Click Chemistry Combined with Nitroxide-Mediated Radical and Cationic Ring Opening

Polymerization: A Versatile Method for Preparation of Well –Defined Block Copolymers

Saber Ibrahim and Brigitte Voit, Institute for Polymer Research Dresden, Germany

Introduction
The azide/alkyne-“click”-reaction has had enormous impact within the field of polymer science. By using click chemistry not only more, but also more
complex molecules and materials can be approached.
Well-defined diblock copolymers consisting of polystyrene (PS) and poly (2-methyl-2-oxazoline) (PMeOX) or polyethyleneimine (PEI) were prepared
using the nitroxide-mediated radical polymerization (NMRP) and Cationic Ring Opening Polymerization (CROP) methods respectively. The number-
average molecular weight and fraction of each segment were precisely controllable by adjusting the monomer/initiator ratio in feed.

N Ph
O O
N Ph N Ph N Ph m
O N Ph
O O N N
n
m NaN 3 m
Ph Ph o Ph
o DMF/50 C
125 C N3

Cl
Cl N3
N PS
N
Prepared Polymer and Copolymer N
AFM Pictures
Polystyrene prepared by nitroxide-mediated PMeOX
radical polymerization bearing a benzyl
chloride on the α-terminus was converted to an
azide by SN2 displacement.
Thermal Analysis
Piperazine was protected to afford its N-Boc
derivatives. This reacted with propargyl
bromide to obtain N-t-Boc propargylpiperazine,
100 6
––––––– Sab 22.001
––––––– Sab 29.001
80 ––––––– Sab 30.001

then Deprotected with trifluroacetic acid 60

40

Deriv. Weight (%/°C)

4

yielded propargyl piperazine. Poly2-methyl-2- (a) (b) 20

Weight (%)
0

Oxazoline was created by cationic ring opening -20

polymerization and terminated with

-40

-60

propargylpiperazine. Block copolymer PS-b-

-80

-100 0
0 200 400 600 800

PMeOX was obtained by 1,3-dipolar

Temperature (°C) Universal V4.3A TA Instruments

cycloaddition reaction between azide group in 0.05

–––––––
–––––––
Sab22.001
Sab29.001
Abkühlen

PS and alkyne group in PMeOX in present of

––––––– Sab30.001

0.00

Cu(I)-catalyzed. Polystyrene-b- (c) (d)

Heat Flow (W/g)

polyethylenimine (PS-b-PEI) was synthesized Atomic Force Microscopy 2.0 μm images of -0.05

by the hydrolysis of the obtained block polystyrene block poly2-methyl-2-oxazoline (PS-b-

PMeox) with diffeent block ratios, (a) 1:6.7 & (b)
-0.10

copolymer PS-b-PMeOX in alkaline medium

overnight. 1:9.3 & (c) 1:0.9 and (d) 1:5.2 -0.15

Exo Down
20 40 60 80
Temperature (°C)
100 120 140
Universal V4.3A TA Instruments

The synthesis of diblock copolymers by

combining predefined polymeric fragments via Conclusion
Poly(alkoxyamine) including PMeOX segments can be used as a
click chemistry was proved. In this situation, macroinitiator for NMRP of styrene. The strategy described here is
the fragments could be completely linked with available for the preparation of a wide variety of well-defined block
copolymer libraries to be readily prepared in the minimum number of
each other and diblock copolymers obtained steps under synthetically robust conditions, and is expected as to be a
exhibited a narrow molecular weight powerful systematic screening tool for the preparation of interesting
phase separated functional polymeric materials with specific metal
distribution. binding ability.
• R.K. O'Reilly, M.J. Joralemon, K.L. Wooley and C.J. Hawker,
Chem Mater 17 (2005), 5976.
• C.J. Hawker, V.V. Fokin, M.G. Finn and K.B. Sharpless, Aust J
Chem 60 (2007), 381.
• P.L. Golas and K. Matyjaszewski, QSAR Comb Sci 26
(2007),1116.
• N.V. Tsarevsky, B.S. Sumerlin and K. Matyjaszewski,
Macromolecules 38 (2005), 3558.
• N.V. Tsarevsky, S.A. Bencherif and K. Matyjaszewski,
Macromolecules 40 (2007), 4439.
• H. Zheng, L.M. Weiner, O. Bar-Am, et al, Bioorg. & Med. Chem.
13 (2005), 773.
• S. Fleischman, H. Komber, D. Appelhans, B. I. Voit, Macromol.
Chem. Phys. 208 (2007), 1050.
Aknowledgement
The author would like to thank his colleague S. Fleishmann , L. Häußler for
TG measurement and GPC experiments were performed by Frau P. Treppe.
Also, We gratefully acknowledge financial support and participate for
scholarship from the Egyptian Ministry for Scientific Research.
Click Chemistry Combined with Nitroxide-Mediated Radical and Cationic Ring Opening
Polymerization: A Versatile Method for Preparation of Well –Defined Block Copolymers
Saber Ibrahim and Brigitte Voit, Institute for Polymer Research Dresden, Germany

Introduction
The azide/alkyne-“click”-reaction has had enormous
impact within the field of polymer science. By using click
N Ph
chemistry not only more, but also more complex
molecules and materials can be approached. O O
Well-defined diblock copolymers consisting of m
polystyrene (PS) and poly (2-methyl-2-oxazoline) N Ph
N N
(PMeOX) or polyethyleneimine (PEI) were prepared n
using the nitroxide-mediated radical polymerization
(NMRP) and Cationic Ring Opening Polymerization
(CROP) methods respectively. The number-average
molecular weight and fraction of each segment were N3
precisely controllable by adjusting the monomer/initiator
ratio in feed.

N PS
N
N
N Ph N Ph
O PMeOX
O
m
Ph Ph
o
125 C
AFM Pictures

Cl
Cl

Thermal Analysis
N Ph 100 6
––––––– Sab 22.001
––––––– Sab 29.001
80 ––––––– Sab 30.001

O 60

40

Deriv. Weight (%/°C)

NaN3
4

m 20

Weight (%)
o Ph
DMF/50 C
0

(a) (b) -20

2
-40

-60

-80

-100 0
0 200 400 600 800

N3 Temperature (°C) Universal V4.3A TA Instruments

0.05

Prepared Polymer and Copolymer

––––––– Sab22.001 Abkühlen
––––––– Sab29.001
––––––– Sab30.001

Polystyrene prepared by nitroxide-mediated radical 0.00

polymerization bearing a benzyl chloride on the α- Heat Flow (W/g)

terminus was converted to an azide by SN2

-0.05

(c) (d)
displacement. Atomic Force Microscopy 2.0 μm images of -0.10

Piperazine was protected to afford its N-Boc

derivatives. This reacted with propargyl bromide to
polystyrene block poly2-methyl-2-oxazoline (PS-b- -0.15

PMeox) with diffeent block ratios, (a) 1:6.7 & (b)

20 40 60 80 100 120 140
Exo Down Temperature (°C) Universal V4.3A TA Instruments

obtain N-t-Boc propargylpiperazine, then Deprotected

with trifluroacetic acid yielded propargyl piperazine.
Poly2-methyl-2-Oxazoline was created by cationic ring
opening polymerization and terminated with
propargylpiperazine. Block copolymer PS-b-PMeOX
was obtained by 1,3-dipolar cycloaddition reaction
between azide group in PS and alkyne group in PMeOX
in present of Cu(I)-catalyzed. Polystyrene-b-
polyethyleneimine (PS-b-PEI) was synthesized by the
hydrolysis of the obtained block copolymer PS-b-
PMeOX in alkaline medium overnight.
The synthesis of diblock copolymers by combining
predefined polymeric fragments via click chemistry was
proved. In this situation, the fragments could be
completely linked with each other and diblock
copolymers obtained exhibited a narrow molecular
weight distribution.
O
N • H. Zheng, L.M. Weiner, O. Bar-Am, et al, Bioorg. & Med. Chem.
a N
RX n R
O n
a) N-propargylpiperazine, 70 - 80 oC.
1:9.3 & (c) 1:0.9 and (d) 1:5.2
Conclusion
Poly(alkoxyamine) including PMeOX segments can
be used as a macroinitiator for NMRP of styrene. The
strategy described here is available for the preparation
O
m
N of a wide variety of well-defined block copolymer
Ph libraries to be readily prepared in the minimum
O
number of steps under synthetically robust conditions,
R N N and is expected as to be a powerful systematic
N N N
n N screening tool for the preparation of interesting phase
O N separated functional polymeric materials with specific
metal binding ability.
o
100 C KOH • R.K. O'Reilly, M.J. Joralemon, K.L. Wooley and C.J. Hawker,
Chem Mater 17 (2005), 5976.
O mN • C.J. Hawker, V.V. Fokin, M.G. Finn and K.B. Sharpless, Aust J
Ph Chem 60 (2007), 381.
O • P.L. Golas and K. Matyjaszewski, QSAR Comb Sci 26
(2007),1116.
• N.V. Tsarevsky, B.S. Sumerlin and K. Matyjaszewski,
R N N
N N N Macromolecules 38 (2005), 3558.
n N • N.V. Tsarevsky, S.A. Bencherif and K. Matyjaszewski,
O N Macromolecules 40 (2007), 4439.
13 (2005), 773.
N N • S. Fleischman, H. Komber, D. Appelhans, B. I. Voit, Macromol.
Chem. Phys. 208 (2007), 1050.
Aknowledgement
The author would like to thank his colleague S. Fleishmann , L. Häußler for
TG measurement and GPC experiments were performed by Frau P. Treppe.
Also, We gratefully acknowledge financial support and participate for
scholarship from the Egyptian Ministry for Scientific Research.
 PS
PS-b-PMeox

4 5 6 7 8 9

Retention time

PS
PS-b-PMeox

polystyrene
Preparation of polystyrene azide 4 5 6 7 8 9
Retention time

Hydrolysis of polystyrene-b-polymethyloxazoline
O

R N N O N
mN N n
+ Ph

Preparation of polymethyloxazoline alkyne

O

O O N
O + m
Cu Catalyst
N3
N Ph
N
N n-1

N N3 O N
Cu Catalyst n

Polystyrene-b-polyethyleneimine
Ph

Monomer/ Conversion Mn,cal Mn, SEC Mw, SEC PDI

4 O 5 6 7 8 9
R N N
Initiator %
O N
m
Ph O
mN N N
N
N
Retention time
O O

N
N N 100oC KOH
n-1 N N
O N
N N n
Ph

H
R N N
mN N N
N
H
N

PS-b-Meox

4 5 6 7 8 9 10
Retention time
Click Chemistry Combined with Nitroxide-Mediated Radical and Cationic Ring Opening
Polymerization: A Versatile Method for Preparation of Well–Defined Block Copolymers
Saber Ibrahim and Brigitte Voit, Institute for Polymer Research Dresden, Germany

Introduction
The azide/alkyne-“click”-reaction has had enormous Size Exclusion Chromatograohy
impact within the field of polymer science. By using click
N Ph
chemistry not only more, but also more complex
molecules and materials can be approached. O O
Well-defined diblock copolymers consisting of m
polystyrene (PS) and poly (2-methyl-2-oxazoline) N Ph
N N
(PMeOX) or polyethyleneimine (PEI) were prepared n
using the nitroxide-mediated radical polymerization
(NMRP) and Cationic Ring Opening Polymerization PS
PS-b-PMeox
(CROP) methods respectively. The number-average
molecular weight and fraction of each segment were N3
4 5 6 7 8 9
precisely controllable by adjusting the monomer/initiator Retention time
ratio in feed. EXP. Monomer/ Conversion Mn,cal Mn, SEC Mw, SEC PDI
Initiator %
PSN3 309 83 6500 7400 8300 1.07

N PS
PMeox 200 79 5000 5800 6200 1.11

N PS-b-PMeox --- 95 12000 12300 14100 1.14

N
N Ph
N Ph PMeOX
O O
m
Ph
Ph
AFM Pictures
o PMeox
125 C

Cl Cl

Thermal Analysis
N Ph
100 6
––––––– Sab 22.001

O
––––––– Sab 29.001
80 ––––––– Sab 30.001

60

NaN3 m 40

Ph

Deriv. Weight (%/°C)

4

o (a) (b)
DMF/50 C
20

Weight (%)
0

-20

2
-40

-60

-80

N3
-100 0
0 200 400 600 800
Temperature (°C) Universal V4.3A TA Instruments

Prepared Polymer and Copolymer 0.05

–––––––
–––––––
–––––––
Sab22.001
Sab29.001
Sab30.001
Abkühlen

Polystyrene prepared by nitroxide-mediated radical 0.00

polymerization bearing a benzyl chloride on the α-

Heat Flow (W/g)
terminus was converted to an azide by SN2 (c) (d) -0.05

displacement. Atomic Force Microscopy 2.0 μm images of polystyrene block

Piperazine was protected to afford its N-Boc poly2-methyl-2-oxazoline (PS-b-PMeox) with diffeent block
-0.10

derivatives. This reacted with propargyl bromide to ratios, (a) 1:6.7 & (b) 1:9.3 & (c) 1:0.9 and (d) 1:5.2 -0.15

obtain N-t-Boc propargylpiperazine, then Deprotected

20 40 60 80 100 120 140
Exo Down Temperature (°C) Universal V4.3A TA Instruments

with trifluroacetic acid yielded propargyl piperazine.

Poly2-methyl-2-Oxazoline was created by cationic ring Conclusion
opening polymerization and terminated with Poly(alkoxyamine) including PMeOX segments can
propargylpiperazine. Block copolymer PS-b-PMeOX O N be used as a macroinitiator for NMRP of styrene. The
was obtained by 1,3-dipolar cycloaddition reaction m
Ph strategy described here is available for the preparation
between azide group in PS and alkyne group in PMeOX O of a wide variety of well-defined block copolymer
in present of Cu(I)-catalyzed. Polystyrene-b- libraries to be readily prepared in the minimum
polyethyleneimine (PS-b-PEI) was synthesized by the R N N
N N N number of steps under synthetically robust conditions,
n
hydrolysis of the obtained block copolymer PS-b- N
and is expected as to be a powerful systematic
PMeOX in alkaline medium overnight. O N
screening tool for the preparation of interesting phase
The synthesis of diblock copolymers by combining separated functional polymeric materials with specific
predefined polymeric fragments via click chemistry was o
100 C KOH metal binding ability.
proved. In this situation, the fragments could be
O mN • R.K. O'Reilly, M.J. Joralemon, K.L. Wooley and C.J. Hawker,
completely linked with each other and diblock
Ph Chem Mater 17 (2005), 5976.
copolymers obtained exhibited a narrow molecular • C.J. Hawker, V.V. Fokin, M.G. Finn and K.B. Sharpless, Aust J
O
weight distribution. Chem 60 (2007), 381.
• P.L. Golas and K. Matyjaszewski, QSAR Comb Sci 26
R N N
N N N (2007),1116.
n N • N.V. Tsarevsky, B.S. Sumerlin and K. Matyjaszewski,
O N Macromolecules 38 (2005), 3558.
O • N.V. Tsarevsky, S.A. Bencherif and K. Matyjaszewski,
Macromolecules 40 (2007), 4439.
N • H. Zheng, L.M. Weiner, O. Bar-Am, et al, Bioorg. & Med. Chem.
a N 13 (2005), 773.
RX n R N N • S. Fleischman, H. Komber, D. Appelhans, B. I. Voit, Macromol.
O n
Chem. Phys. 208 (2007), 1050.
Aknowledgement
The author would like to thank his colleague S. Fleishmann , L. Häußler for
a) N-propargylpiperazine, 70 - 80 oC. TG measurement and GPC experiments were performed by Frau P. Treppe.
Also, We gratefully acknowledge financial support and participate for
scholarship from the Egyptian Ministry for Scientific Research.