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DOI: 10.1002/masy.200750505
Introduction
Polymers displaying phase transitions in
aqueous solution from a hydrophilic to
hydrophobic state are of widespread interest as smart biomedical materials.[1]
The prototypical polymer in this class is
poly(N-isopropylacrylamide) (PNIPAAm)
and co-polymers derived from this basic
material. One interesting feature of these
polymers is that the lower critical solution
transition (LCST) is observed in water
around body temperature[2] i.e. 37 8C.
These materials are currently being used
in a variety of applications including cell
attachment, drug release, separation membranes and tissue engineering.[36]
The LCST transition in PNIPAAm can
be triggered using a variety of external
stimuli such as temperature, pH and solvent
composition. The two main effects responsible for the LCST are hydrophobic and
1
Experimental Part
Reagents and Solvents
All the reagents and solvents used for the
synthesis and the characterisation of the
co-monomers and co-polymers were purchased from Sigma Aldrich and used as
received except for N-isopropylacrylamide
(NIPAAm) and 4,40 -azoisobutyronitrile
33
34
H 2C
CH
H2C
NH
H3C
CH
NH
CH2 n
CH3
O
OH
n = 3 : -acryloylaminobutyric acid
n = 5 : 6-acryloylaminohexanoic acid
n = 10 : 11-acryloylaminoundecanoic acid
N-isopropylacrylamide
Figure 1.
Chemical structure of monomer and co-monomers used for the polymer synthesis.
(AIBN) which were purified by re-crystallisation from hexane and methanol respectively.
H2C
NH2
CH
CH2 n
+
O
CH
Schotten-Baumann
NH
CH2 n
conditions
Cl
O
HCl
OH
O
acryloyl chloride
amino acid
OH
co-monomer
Figure 2.
Scheme of the route used for the synthesis of the co-monomers.
Copyright ! 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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35
H2C
H2C
CH
NH
H3C
NIPAAm
+
CH3
CH
*
isopropanol
NH
CH2 n
CH
NH
CH
OH
co-monomer
NH
AIBN
CH2
H3C
O
CH3
O
OH
co-polymer
Figure 3.
Scheme of the route used to synthesise the co-polymers.
Copyright ! 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.ms-journal.de
36
Table 1.
Structure nomenclature, composition, weight-average molecular weight and polydispersity of the copolymers
synthesised.
NIPAAM/co-monomer
feed molar ratio
n=3
*
CH
NH
n=5
CH
NH
CH3
O
CH
CH2
H3C
n = 10
CH
NH
CH3
OH
CH
CH
NH
OH
CH2
H3C
CH3
10
OH
CP(n 3)-9-COOH
CP(n 3)-12-COOH
CP(n 5)-6-COOH
CP(n 5)-9-COOH
CP(n 5)-12-COOH
CP(n 10)-6-COOH
CP(n 10)-9-COOH
CP(n 10)-12-COOH
8.9:1
11.6:1
5.6:1
9.2:1
11.3:1
6.2:1
9.1:1
11.5:1
6200
3800
2400
5700
3500
7900
6500
10100
2.2
1.2
1.8
1.4
1.3
1.4
2.4
1.7
NH
Nomenclature
6:1
9:1
12:1
NIPAAm/co-monomer
molar composition
6:1
9:1
12:1
Molecular weight (Mw)/Da
6:1
9:1
12:1
Polydispersity (Mw/Mn)
6:1
9:1
12:1
NH
CH2
H3C
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Tg [C]
37
135
130
125
120
115
110
105
100
95
0
10
Figure 4.
Co-polymers Tg vs. co-monomer chain length for different NIPAAm/co-monomer molar ratios.
3.5
Absorbance [a.u.]
3
2.5
2
cooling
heating
1.5
1
0.5
0
20
23
26
29
32
35
38
41
44
47
50
Temperature [C]
Figure 5.
UV/Vis absorbance spectra (600 nm) of a PNIPAAm solution (10 mg ml"1) during a heating/cooling cycle (1 8C
min"1) from room temperature to 50 8C.
Copyright ! 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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cooling
5
4
3
38
2
1
0
-1 20
23
26
29
32
35
38
41
44
47
50
-2
-3
-4
-5
heating
Temperature [ C]
Figure 6.
Microcalorimetry curve of a PNIPAAm solution (10 mg ml"1) during a heating/cooling cycle (1 8C min"1) from
room temperature to 50 8C.
Table 2.
LCSTs in heating/cooling.
LCST temperatures (heating/cooling)/8C
Molar ratio
12:1
9:1
6:1
n3
34.9/33.3
34.5/33.2
n5
30.1/27.5
28.6/26.0
27.8/23.0
n 10
19.0/17.8
16.5/16.8
12.3/11.5
PNIPAAm
38.9/36.6
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39
no.CH2=10
no. CH2=5
no. CH2=3
40
35
LCST [C]
30
25
20
15
10
0
10 11 12 13 14 15 16 17
Figure 7.
LCST temperature vs. co-monomer content.
Conclusions
The synthesis of acrylic acid derivate
co-monomers with aliphatic spacers was
successfully achieved with good yields
(6080%). Temperature sensitive co-polymers were prepared by the copolymerization
of N- isopropylacrylamide (NIPAAm) with
varying amounts of acrylamide derivates
bearing carboxylic groups attached to
spacers with different chain length. We have
45
40
35
LCST [C]
30
25
20
15
10
5
0
0
10
Figure 8.
LCST temperature vs. co-monomer chain length.
Copyright ! 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.ms-journal.de
40
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