EUROPEAN

POLYMER
European Polymer Journal 43 (2007) 3042–3049
JOURNAL
www.elsevier.com/locate/europolj

Synthesis of PDMAEMA–PCL–PDMAEMA
triblock copolymers
Shaheen Motala-Timol, Dhanjay Jhurry *

Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, Mauritius

Received 14 December 2006; received in revised form 9 March 2007; accepted 15 March 2007
Available online 1 May 2007

Abstract

The synthesis of ABA triblock copolymers of the type PDMAEMA–PCL–PDMAEMA was achieved by atom transfer
radical polymerization (ATRP) of DMAEMA using difunctional polycaprolactone (PCL) as macroinitiator. First, ring-
opening polymerization (ROP) of e-caprolactone (e-CL) was carried out in the presence of 1,2-diaminoethane/tin (II) octa-
noate. Dihydroxy PCL thus obtained was end-functionalized in a quantitative manner using 2-bromoisobutyryl bromide.
The resulting Br–PCL–Br was used as macroinitiator in the ATRP of DMAEMA leading to triblock copolymers with PCL
as the central block and PDMAEMA sequences of different lengths. NMR and SEC analyses confirmed the formation of
ABA triblocks.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Poly(e-caprolactone) macroinitiator; Atom transfer radical polymerization (ATRP); DMAEMA; Block copolymers

1. Introduction (PMMA), polypropylene oxide [7] (PPO), polybutyl

Amphiphilic di- and tri-block copolymers con-
taining tertiary amine methacrylic sequences are
interesting due to their micellar properties in aque-
ous media which can be modified by salt concentra-
tion, temperature and pH changes. Their syntheses
have been extensively reported in the literature
[1–4]. Well-defined amphiphilic block copolymers
comprising of PDMAEMA as the hydrophilic
block(s) and different polymers as the hydrophobic
blocks(s), such as polymethyl methacrylate [5,6]
*
Corresponding author. Tel.: +230 454 1041; fax: +230 465
6928.
E-mail address: djhurry@uom.ac.mu (D. Jhurry).
methacrylate [8] (PBMA), polyethylene glycol [9]
(PEG) and PCL [10,11] have been synthesized via
living polymerization techniques using the macro-
initiator approach. Zhang and Matyjaszewski [6]
have thus reported the synthesis of di- and tri-
blocks PMMA and PDMAEMA copolymers using
a PMMA–Cl macroinitiator to polymerize DMA-
EMA by ATRP. The PMMA macroinitiator with
a chlorine end-group was prepared by ATRP of
methyl methacrylate using p-toluenesulfonyl chlo-
ride as the initiator and CuCl/4,4 0 -di(5-nonyl)-2,2 0 -
bipyridyl as catalyst. Cl–PMMA–Cl difunctional
macroinitiator was also obtained by ATRP under
similar conditions using a difunctional initiator,
1,2-bis-(2-bromopropionyloxy)ethane. The active
chlorine at the end(s) of the PMMA chains then

0014-3057/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.03.052
 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049
initiated polymerization of DMAEMA, leading
to amphiphilic PMMA–PDMAEMA and PDMA-
EMA–PMMA–PDMAEMA copolymers. Dynamic
light scattering studies showed that the size of the
micelles of such types of block copolymers in
aqueous media increased with the degree of
polymerization of the PDMAEMA blocks [6].
Macroinitiators can also be prepared by the chemi-
cal modification of the functional end-group of
polymer chains. Thus, PDMAEMA–PEG–PDMA-
EMA triblocks have been synthesized by ATRP
of DMAEMA using Br–PEG–Br as macroinitiator
[9], which was prepared by the reaction of
HO–PEG–OH and 2-bromoisobutyryl bromide. In
a similar fashion, we synthesized PDMAEMA–
PCL diblock copolymers by ATRP using PCL–Br
[12] as macroinitiator. The latter was synthesized
by reacting 2-bromoisobutyryl bromide with PCL–
OH, which was obtained by the ROP of e-CL in
the presence of a Schiff’s base aluminium complex
(HAPENAlOiPr). PDMAEMA–PCL block copoly-
mers were also synthesized by Jakubowski et al. [11]
using a combination of ROP and ATRP. In this
method, 2-hydroxyethyl 2-bromoisobutyrate, an
initiator with dual functionality for ATRP and
ROP, was used for polymerization of e-CL in the
presence of tin (II) octanoate. The resulting
bromo-end functionalized PCL was then used as
macroinitiator in the ATRP of DMAEMA.
PDMAEMA–PCL block copolymers are interesting
as they are biodegradable and exhibit amphiphilic
properties. Block copolymers with PDMAEMA
segments can also synthesized by other controlled
polymerization techniques using macroinitiators.
Thus, PDMAEMA–PPO–PDMAEMA triblocks
have been synthesized by oxyanion-initiated poly-
merization [7]. A difunctional potassium alcoholate,
prepared from dihydroxy-poly(propylene oxide)
and potassium hydride, was used as initiator
in the polymerization of DMAEMA leading to
triblocks.
In this paper, we report on the synthesis of ABA
triblock copolymers consisting of PCL as central bio-
degradable block and PDMAEMA hydrophilic
blocks at the two ends using an efficient method. This
consists first in carrying out the ROP of e-CL in the
presence of 1,2-diaminoethane/tin (II) octanoate
(SnOct2) initiator system so as to generate an a,x-
di-hydroxy-PCL. The latter is then transformed into
a dibromo–PCL, which is used as macroinitiator for
the polymerization of DMAEMA by ATRP.
3043
2. Results and discussion
2.1. ROP of e-CL using 1,2-diaminoethane/SnOct2 as
initiating system
2.1.1. Kinetics and polymerization mechanism
a,x-hydroxypolycaprolactone can be synthesized
by the ROP of e-CL using a difunctional initiator in
the presence of tin (II) octanoate (SnOct2) (Scheme
1). The latter has been used for years for the ROP of
lactones as it provides high reaction rate, high con-
version, high molar masses, and is approved by the
FDA. The ROP of e-CL was here investigated in the
presence of 1,2-diaminoethane/SnOct2 as initiator
system. Low–molar–mass PCL were synthesized
for a more efficient end-functionalization thereafter.
For kinetic comparisons, 1,2-ethanediol/SnOct2 was
also used as initiator for e-CL polymerization.
Fig. 1 shows the semi-logarithmic plot of ln[Mo]/
[Mt] for the bulk polymerization of e-CL at 120 °C
in the presence of both initiator systems. An induc-
tion period was observed for both polymerizations
but was more pronounced with the 1,2-diamino-
ethane/SnOct2 system. Indeed, monomer conversion
after 1 h corresponded to only 4%. These induction
periods pointed towards formation of a complex
(Fig. 2) between the functional initiators and SnOct2
prior to the ROP of e-CL, as previously reported
[13–18]. Indeed, for lactone polymerization using
SnOct2 in the presence of an alcohol, Penczek and
co-workers [13–16] have proposed the formation
of a complex between SnOct2 and the alcohol, prior
to coordination/insertion with the lactone and poly-
merization. Recently, our group [17,18] conducted
NMR studies on the ROP of e-CL in the presence
of tin (II) octanoate and mono- or difunctional ini-
tiators (butanol, butylamine and ethanolamine).
Our results are also in favor of the formation of a
complex prior to ring-opening polymerization. For
instance, with ethanolamine, the results showed that
polymerization proceeded first through complexa-
tion of both hydroxyl and amino groups of ethanol-
amine onto tin (II) octanoate. Polymerization then
occurred via insertion of e-CL into Sn–O and Sn–
N dative bonds as evidenced by the presence of ester
and amide signals in the carbonyl region, thus lead-
ing to an a,x-dihydroxy-PCL.
A longer induction period was observed with
1,2-ethanediamine, as compared to the diol, indicat-
ing that the interaction between SnOct2 and the
diamino initiator is much stronger than that
3044 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049

O O
HO H
O NH2 (CH2)2 NH2 O N PCL
PCL N O OH
H
Sn Oct2 O

ε -CL O
Br , 80oC, 5 h (-2HBr)
2 Br
H3C CH3

H3C CH3 O O
H
O O N PCL Br
Br PCL N O O
H H3C CH3
O O
Br-PCL-Br

CH3
O CH3
N , CuBr, Bpy
O CH3

O
H
PDMAEMA O N PCL
PCL N O PDMAEMA
H
O

Scheme 1. Synthesis of triblock P(DMAEMA–CL–DMAEMA) copolymer.

H H
O
N NH
H
O
Sn
H O
H
O N N
H H

Fig. 2. Proposed structure of complex formed between SnOct2

and 1,2-diaminoethane.

reactions by 1H NMR showed that ROP of e-CL

Fig. 1. Plot of ln[Mo]/[Mt] against time for e-CL polymerization
using difunctional initiators in the presence of SnOct2 at 120 °C.
between 1,2-ethanediol and SnOct2, nitrogen being
a better electron donor than oxygen. Insertion
of e-CL into Sn–O bond is thus easier than into
Sn–N bond. Similar results were obtained by
Lochee [17] for the ROP of e-CL using butan-1-ol
and butylamine in the presence of SnOct2. Model
using butanol/SnOct2 complex occurred at room
temperature, whereas in the presence of butyl-
amine/SnOct2 complex, polymerization started only
upon heating at 110 °C.
After the induction periods, the polymerization
rate was found to be first order with respect to
monomer concentration up till high conversions
(>80%), for both systems. At higher conversion
and high reaction temperature, side-reactions, such
as transesterification reactions, are a well-known
feature in tin (II) catalyzed polymerizations, leading
to polymers with broader mass distributions. The
diaminoethane/SnOct2 system was preferred over
the diol/SnOct2 system as the experimental values
of molar mass at high conversion were in better
agreement with the predicted values, implying a bet-
ter control of the ring-opening polymerization.
 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049
2.1.2. NMR of a,x-dihydroxy-PCL
Polymerization of e-CL using 1,2-diamino-
ethane/SnOct2 yield a,x-dihydroxy-PCL, after pre-
cipitation in acidified methanol, as confirmed by
1
H NMR (Fig. 3A).
The molar mass was calculated from the NMR
spectra by comparing the intensities of the hydroxy-
methylene end-group (Hg) at 3.6 ppm to the
methyl group (Hf) of the main PCL chain.
M 1H
n
NMR
(4100) was quite close to the expected
molar mass of PCL (M calc: n ¼ 3900) obtained at
M/I = 40 at 85% conversion. Furthermore, the
intensity of the signal corresponding to the N-meth-
yleneamide groups (Ha) at 3.35 pm was equal to
that of the hydroxymethylene end-groups (Hg), indi-
cating that all the co-initiator, NH2CH2CH2NH2, is
used up in polymerization. The final polymer has
about 18 CL units (DPn = 36) attached to each
amino group.
13
C NMR spectrum of PCL showed the presence
of 3 signals in the carbonyl region, together with
Fig. 3. 1H NMR (CDCl3) of (A) PCL synthesized using NH2CH2CH2NH2/SnOct2 as initiating system at (conversion = 85%), (B) Br–
PCL–Br and (C) PDMAEMA–PCL–PDMAEMA triblock copolymer.
3045
that of unreacted e-CL at 176.4 ppm. The signal at
173.7 ppm corresponded to C@O in the main PCL
chain, while that at 173.9 ppm was assigned to the
carbonyl in the last caprolactone unit [19]. The sig-
nal at 174.3 ppm was assigned to the carbonyl of
amide group, as a result of insertion of e-CL into
the Sn–N bond.
2.2. Synthesis and characterization of Br–PCL–Br
a,x-dihydroxy-PCL (M 1H n
NMR
¼ 4100) was trans-
formed into Br–PCL–Br by reacting with 2-bromo-
isobutyryl bromide (Scheme 1). The polymer was
isolated by precipitation in methanol and character-
ized. End-functionalization was confirmed by 1H
NMR (Fig. 3B). The anchoring of the bromoisobu-
tyl moiety was indicated by the downfield shift of
the hydroxymethylene of PCL (Hg) from 3.62 ppm
to 4.21 ppm (Hi) and by the presence of a sharp
0
singlet (Hh,h ) at 1.92 ppm, corresponding to the
two methyl groups adjacent to the bromine atom.
3046 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049

The intensities of the signals corresponding to the titatively end-functionalised by the bromo
methylene ester (Hi) and to the N-methyleneamide compound. No singlet due to unreacted 2-bromo-
(Ha) were similar and indicated that the end- isobutyryl bromide is observed. 1H NMR results
capping was quantitative. Also, comparison of also indicated an increase in molar mass (M NMR
n Þ
the integrals of PCL peak Ha to that of Hh which of Br–PCL–Br compared to the dihydroxy-PCL
corresponds to the methyl groups of the 2-bromo- probably due to elimination of small chains upon
isobutyryl group, confirms that PCL has been quan- precipitation in methanol.

Table 1
Characterization of triblock copolymers by 1H NMR and SEC
a b c d
Copolymer M/I Polymerization time (h) M Theo
n M 1H
n
NMR
M SEC
n M w M SEC
n

1 30 3 13,700 13,400 19,000 1.73

2 60 7 23,000 24,300 43,900 1.65
3 120 18 42,000 47,700 52,500 1.61
4 240 24 79,000 95,800 67,700 1.67
a
I = Br–PCL–Br (M NMR
n ¼ 4300, M SEC
n ¼ 4000).
b
M 1H
n
NMR
¼ ½2  M=I theo
 M r (DMAEMA)] + 4300.
c
M 1H
n
NMR
¼ ½2  M=I NMR  M r (DMAEMA)] + 4300.
d
SEC in DMF/LiBr, using polystyrene as standards.

a
CH3 O
b k i
O
m
c j h PDMAEMA
x l y
d O
O
e
f
g N g'
H3C CH3

13
Fig. 4. C NMR (CDCl3) of triblock copolymer, PDMAEMA-b-PCL-b-PDMAEMA.
 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049
2.3. Synthesis of triblock copolymers: PDMAEMA–
PCL–PDMAEMA
The dibromo-PCL (M 1H n
NMR
¼ 4300, DPn = 38,
SEC
M n =M w ¼ 1:25) was used as macroinitiator in
the presence of CuBr/bipyridine (Scheme 1) for
the bulk ATRP of DMAEMA. Polymers of various
molar masses were obtained by varying the macro-
initiator concentration (Table 1).
1 to be taken with care since PDMAEMA polymers
H and 13C NMR spectra confirmed the presence
of both polymer sequences (Figs. 3C and 4). The
molar masses of the copolymers were calculated
by comparing the intensity of the methylene protons
(Hn) of PDMAEMA at 2.56 ppm to the combined
intensities of the methylene protons of PCL and
PDMAEMA at 4.0 ppm (Hf and Hm). It is observed
that the Mn values of the copolymers as determined
by NMR are significantly higher than the calculated
ones, implying that the efficiency of the macroiniti-
ator decreases as its concentration is lowered. 13C
NMR analysis (Fig. 4) showed signals at
173.7 ppm and at 176–178 ppm, assigned, respec-
tively to the carbonyl of PCL and to that of
PDMAEMA.
The copolymers exhibited monomodal mass dis-
tributions and a shift to higher molar mass as com-
pared to the macroinitiator, which is a good
evidence of the formation of copolymers (Fig. 5).
The molar mass distributions of the various triblock
Fig. 5. SEC traces of macroinitiator Br–PCL–Br and copolymer
3, P(DMAEMA-b-CL-b-DMAEMA), in DMF/LiBr as eluent,
using polystyrene standards.
3047
Table 2
Cloud points of triblock copolymers
Copolymer Temperature (°C)
2 68
3 72
4 78
copolymers are approximately 1.7 but this value has
are known to be difficult to characterize by SEC
due to adsorption of amino-end-groups onto the
column [20].
The cloud points of a few copolymers as listed in
Table 2 are found to be in the range 68–78 °C. The
values reported are well above the LCST of PDMA-
EMA homopolymer (40–50 °C) in water. The cloud
points were here measured in the presence of NaCl
generated in situ during the dissolution of the
copolymers but the salt may not be responsible for
the relatively higher cloud points observed. How-
ever, it is to be noted that the pH values of the
copolymer solutions were in the range 6.9–7.0,
which tend to indicate the presence of residual
hydrochloric acid as neutral (co)polymers contain-
ing DMAEMA give in water a pH around 8. This
could have lead to the partial ionization of PDMA-
EMA and account for the high cloud point values.
Moreover, we observe under our experimental
conditions an increase in the cloud points as the
length of the PDMAEMA blocks increase, indicat-
ing an enhanced stabilization of the micellar struc-
tures. A clearer understanding of the micellar
structure and behaviour should be obtained by
DLS.
3. Conclusion
Triblock copolymers consisting of a central PCL
sequence with PDMAEMA sequences attached at
the two ends have been successfully achieved in a
three-step pathway. A good understanding of the
polymerization of e-CL in the presence of tin (II)
octanoate in combination with a diamine through
kinetic and mechanistic studies was instrumental
in preparing well-defined dihydroxy-PCL. Its quan-
titative transformation into dibromo-PCL and use
of the latter as macroinitiator for the polymeriza-
tion of DMAEMA by ATRP lead to the triblock
architecture. The preparation of a range of triblock
copolymers with polylactides (PLA) of varying
lengths as central blocks is currently underway
3048 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049
and a detailed study of the assembly of triblock
DMAEMA–polyester–DMAEMA chains is also
being carried out.
4. Experimental section
4.1. Materials
2-Dimethylaminoethyl methacrylate (DMA-
EMA) (99%) was passed through a short column
of basic alumina before use. e-caprolactone (e-CL)
(99%, Aldrich) was dried over CaH2 for 48 h and
was distilled under reduced pressure and kept under
argon. Tin (II) octanoate was distilled under reduced
pressure and stored under argon. 2-Bromoisobutyryl
bromide, copper (I) bromide (CuBr), 2,2-bipyridine
(Bpy) and petroleum ether were used as received
from Aldrich. Methanol was refluxed over Mg/I2
and distilled. 1,2-ethanediamine and 1,2-ethanediol
were distilled under vacuum prior to use.
4.2. ROP of e-CL
1,2-Ethanediamine (0.06 g, 1 mmol) and SnOct2
(8 mg, 0.02 mmol) was added to e-CL (4.56 g,
40 mmol) in a glass tube equipped with a rubber
septum. The solution was purged by bubbling nitro-
gen for 15 min. Polymerization was carried out at
120 °C and after the required polymerization time,
crude samples were analyzed by 1H NMR to deter-
mine percentage conversion. At 85% conversion
(t = 6.5 h), reaction was stopped and the polymer
was precipitated in cold acidified methanol. Dihy-
droxy-PCL thus obtained was dried under vacuum.
1
H NMR (CDCl3): d (ppm) = 1.32–1.41 (m,
–(CH2)2–CH2–(CH2)2–O–), 1.53–1.66 (m, –CH2–
CH2–CH2–CH2–CH2–O–), 2.26–2.32 (t,–CH2–
(CH2)4–O–), 3.35 (s, –NH–(CH2)2–NH–), 3.60–
3.64 (t, –CH2–OH), 4.00–4.06 (t, –CO–(CH2)4–
CH2–O–).
13
C NMR (CDCl3): d (ppm) = 24.8 (–(CH2)2–
CH2–(CH2)2–O–), 25.7 (–CH2–CH2–(CH2)3–O),
28.5 (–(CH2)2–CH2–(CH2)2–O), 34.8 (–CH2–
(CH2)4–O), 40.4 (–NH–(CH2)2–NH–a), 62.6
(–CH2–OH), 64.3 (–CO–(CH2)4–CH2–O–), 173.7,
173.9 (CO), 174.3 (–CO–NH).
4.3. Synthesis of Br–PCL–Br
2-Bromoisobutyryl bromide (0.46 g, 2 mmol) was
added to HO–PCL–OH (2.0 g, 0.49 mmol) in a glass
tube. The reaction was carried out under nitrogen
with constant stirring at 80 °C for 5 h. The product
was then washed with cold methanol to eliminate
unreacted 2-bromoisobutyryl bromide and the
white precipitate was dried under vacuum.
1
H NMR (CDCl3): d (ppm) = 1.31–1.41 (m,
–(CH2)2–CH2–(CH2)2–O–), 1.58–1.69 (m, –CH2–
CH2–CH2–CH2–CH2–O–), 1.92 (s, –C(CH3)2–Br),
2.27–2.33 (t, –CH2–(CH2)4–O–), 3.37 (s, –NH–
(CH2)2–NH–), 4.02–4.08 (t, –(CH2)4–CH2–O–),
4.09–4.11 (t, CH2–O–COC(CH3)2Br).
13
C NMR (CDCl3): d (ppm) = 24.8 (–(CH2)2–
CH2–(CH2)2–O–), 25.7 (–CH2–CH2–(CH2)3–O–),
28.5 (–(CH2)3–CH2–CH2–O–), 31.1 (–C(CH3)2Br),
34.8 (–CH2–(CH2)4–O–), 40.5 (–NH–(CH2)2–NH–),
64.3 (–CO–(CH2)4–CH2–O–), 66.0 (–C(CH3)2Br),
171.9 (–COC(CH3)2Br), 173.7 (–CO–(CH2)5–O),
174.3 (–CO–NH–).
4.4. Polymerization of DMAEMA
Br–PCL–Br (0.2 g, 0.055 mmol) was dissolved in
DMAEMA (0.85 g, 5.5 mmol) in a glass tube
equipped with a Rotaflo at ambient temperature.
CuBr (8 mg, 0.055 mmol) and Bpy (16 mg,
0.11 mmol) were added and the mixture was
degassed by 3 vacuum/nitrogen cycles. Polymeriza-
tion was carried out at 60 °C. The product was then
dissolved in THF and recovered by precipitation in
cold heptane. After drying to constant mass, con-
version was determined by gravimetry. Copper
catalyst was removed by passing a solution of
copolymer in THF through a column of basic alu-
mina, before characterization.
1
H NMR (CDCl3): d (ppm) = 0.84–1.05 (–CH2–
C(CO)–CH3), 1.32 (m, –(CH2)2–CH2–(CH2)2–O–),
1.59 (m,–CH2–CH2–CH2–CH2–CH2–O–), 1.76–
1.86 (–CH2–CO–CH3), 2.24 (–N(CH3) + –CH2–
(CH2)4–O–), 2.53 (–CH2–N(CH3)), 4.00 (–O–CH2–
CH2–N– + –(CH2)4–CH2–O–).
13
C NMR (CDCl3): d (ppm) = 16.9, 19.1 (–CH2–
C(CO)–CH3), 24.7 (–(CH2)2–CH2–(CH2)2–O–),
25.6 (–CH2–CH2–(CH2)3–O–), 28.4 (–(CH2)3–
CH2–CH2–O–), 34.2 (–CH2–(CH2)4–O–), 44.9–45.2
(–CH2–CO–CH3), 45.8 (–N(CH3)), 54.9–55.1
(–CH2–C(CO)–CH3), 57.3 (–CH2–N(CH3)), 63.1
(–O–CH2–CH2–N–), 64.2 (–CO–(CH2)4–CH2–O–),
173.7 (CO PCL), 176.6–177.8 (CO PDMAEMA).
4.5. Characterization
1
H and 13C NMR were recorded in CDCl3 as sol-
vent on a 250 MHz Bruker Electrospin Spectrome-
 S. Motala-Timol, D. Jhurry / European Polymer Journal 43 (2007) 3042–3049
ter at ambient temperature. Number-average molar
masses and molar mass distributions were deter-
mined by size exclusion chromatography (SEC) on
a PSS apparatus equipped with an RI detector using
one Gram Linear column. DMF/LiBr (1 g/L) was
used as eluent at a flow rate of 1 ml/min. Calibra-
tions were performed using polystyrene standards.
4.6. Determination of cloud points of triblock
copolymers
The copolymer samples were insoluble in pure
water. To obtain clear solutions, they were first
immersed in pure water and aqueous hydrochloric
acid was added dropwise until a pH of 3. The
copolymer was stirred in acidic medium for about
half an hour before the pH was adjusted with
aqueous NaOH until a clear solution was obtained.
For all copolymer samples, pH at complete dissolu-
tion was recorded in the range 6.9–7.0. Capped glass
tubes containing clear copolymer solutions (4% w/v)
were then immersed without prior purification in a
thermostable bath. The temperature was increased
by 1 degree increment and the cloud point tempera-
ture was measured at the first sign of turbidity.
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