Synthesis and Characterization of Well-Defined block Copolymers by

Combing Controlled Radical and Cationic Polymerization 

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

Strategy and Scientific Goal

N
Ga
N Custom-made
Precursoren Ammonophile
Characterization
N block copolymer 3 1 0 S A B 2 9 (1 4 .0 4 .0 8 ) C D C L 3 _ 0 0 0 0 0 0 F ID
Al2(NMe2)6, Ti(NMe2)4 ...
architectures 1 0 0 S A B 3 9 1 0 .0 6 .0 8 C H C L 3 _ 0 0 0 0 0 0 F ID
0.13
Y
NH3 Ammonolysis 0.12
0.15
m

NMR
0.11
NR2
NR2 H 0.10

Normalized Intensity
R2N Ga X N CH2 CH2 N CH2 CH2 0.09
R2N NH Ga
NR2 H n
0.08 0.10

Normalized Intensity
Ga HN
NH 0.07
R2N NR2
Ga Ga N Ga 0.06
Ga
N N H Electrostatic stabilizer Sterische Stabilisierung 0.05
H H NR2
- - -- - - -- 0.04
0.05

- - - -
- - - -
0.03

- - - - 0.02

0.01

Amphiphiles Polymer 0
0
4.12 27.53 4.5 4.0 3.5 3.0 2.5 2.0 1.5
Chemical Shift (ppm)

Ga(NR2)3 Kristallisation Formgebung 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
Chemical Shift (ppm)

Sol GPC
NH3 Hybridmaterial
„Ga2(NH)3“

Co-ordination of the Precursoren to amino groups of the polymer and following ammonolysis. The structure 

of the polymer is used, in order to make a purposeful localization possible of the nitride oil in the ammonophilen 
domains of the polymer.

Ga
Y

m
Thermal Analysis
Ga

 
Ga
Ga Ga Ga R 2N NR2
Ga Ga NH3
Ga 100 6 0.05
N ––––––– Sab 22.001 ––––––– Sab22.001
Ga Ga X N
––––––– Sab 29.001 ––––––– Sab29.001
Abkühlen
––––––– Sab 30.001
Ga n
H Ga2(NH)3 80 ––––––– Sab30.001

60

Ammonolysis of the preliminary stages and subsequent stabilization by adsorption of polymers  40

4
0.00

at the surfaces of the nitride brine.

Deriv. Weight (%/°C)

•Control of particle size and morphology
20

Heat Flow (W/g)

Weight (%)
0

• study nitride brine -20
-0.05

- - -- - - -- -40
2

- - - -
- - -0.10

- - - - - -
-60

NR2 Polymer-
NR2 -80
R 2N Ga adsorption
R 2N NH Ga -100 0
NR2
Ga HN 0 200 400 600 800 -0.15
NH Universal V4.3A TA Instruments 20 40 60 80 100 120 140
R 2N Temperature (°C)
Ga Ga N Ga NR2 Exo Down Temperature (°C) Universal V4.3A TA Instruments
Ga
N N H
H H NR2
Sol

Prepared Polymers and Copolymer

N N
O O
m m
O N
Synthesis of macroinitiator based on 2-methyl-2- oxazoline by CROP
preparation of polystyrene-b-polymethyl-2-oxazoline block 
   copolymer by NMRP
Polystyrene-b-polyethylenimine block copolymer via alkaline  N
H
N
N N
hydrolysis HN n
HN n
N
N O
HN n

The copolymer of polystyrene-block-poly(ethyleneimine) (PS-b-PEI) was 
Results and Disscusion   prepared, the synthesis process involved ring-opening polymerization (ROP) 
and nitroxide-mediated polymerization (NMP). The ability of modified 
alkoxyamine to initiate ring-opening polymerization of methyl-2-oxazoline 
was evaluated. Also, the polymerization of methyl-2-oxazoline by ordinary 
80 100 4 alkyl chloride was investigated to compare with alkoxyamine intiator and 
70 3,5
80 enhanced the effect of the initiator size on the efficiency of monomer 
Conv e rsion %

60 3
Conversion, %.

reactivity, as shown in Figure1.
ln(M 0/M )

50 60 2,5
40 2
30 40 1,5 N-(1-(4-(chloromethyl)phenyl)ethoxy)-N-tert-butyl-2-methyl-1-
benzylchloride
20
10
alkoxyamine 20
1
0,5
phenylpropan-1-amine was used to synthesis polymethyl-2-oxazoline, which 
0
0 50 100 150 200
0 0 applied as a alkoxyamine macro-initiator for styrene via nitroxide-mediated 
5 10 15 20 25
Tim e, (m in). Reaction time (hr.) polymerization to prepared polystyrene-b-polymethyl-2-oxazoline block 
copolymer with different block ratios. On the other hand, The efficiency of 
Fig.1. Methyl-2-oxazoline conversion in the present  Fig. 2. First-order Kinetics plots of monomer  alkoxyamine initiator was compared with alkoxyamine macrointiator, as 
of Benzyl chloride and Alkoxyamine initiators vs.  conversion and ln(Mo/M) as a function of 
time of reaction at 80oC.  reaction time for the polymerization of styrene by 
shown in Figure3. The kinetics of styrene polymerization reaction with 
polymethyl-2-oxazoline at 120oC.  alkoxyamine initiator was examined, as shown in Figure 4.  Furthermore, PS-
90
b-PEI was synthesised by the hydrolysis of obtained block copolymer PS-b-
PMeOX  in alkaline medium overnight.  
10
80 80

70
70 8
Conversion, %

60
60
50
Conversion, %

6
40
ln(Mo/M)

50

30 40 4
20
Alkoxyamine initiator 30
10
Alkoxyamine Macroinitiator 2
0 20

0 200 400 600

10 0
0 100 200 300 400 500
Tim e, m in.
Time, Min.

Fig.3. Styrene conversion in the present of  Fig. 4. First-order Kinetics plots of monomer  Aknowledgement

alkoxyamine initiator and Alkoxyamine macroinitiator  conversion and ln(Mo/M) as a function of reaction time  We greatfully acknowledge finicial support and participite for schoolarship from the Egyptian
polymethyl-2-oxazoline vs. time of reaction at 120oC.  for the polymerization of styrene by Alkoxyamine 
initiator at 120oC.  State Ministry for Scientific Research.