Thermally crosslinkable poly(N-isopropylacrylamide) copolymers: Synthesis

and characterization of temperature-responsive hydrogel

Wen-Ju Chuang a, Wen-Yen Chiu a, b, c, *, Horng-Jer Tai d
a
Institute of Polymer Science and Engineering, National Taiwan University, Taipei, Taiwan, ROC
b
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan, ROC
c
Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan, ROC
d
Department of Chemical Engineering, I-Shou University, Kaohsiung, Taiwan

a b s t r a c t

Thermally crosslinkable copolymers of N-isopropylacrylamide (NIPAAm) and N-Methylol acrylamide

(NMA), a thermal crosslinker, were prepared by redox polymerization. The aqueous solutions of the
copolymer were temperature responsive, and they showed phase separation behavior. The corre-
sponding phase transition temperatures were detected by UVevisible spectroscopy and differential
scanning calorimetry (DSC). The cloud points increased with increasing content of NMA from 32
C of
pure polyNIPAAm to 48
C for poly(NIPAAm-co-NMA) with 30 mol% NMA. The crosslinking capability of
Keywords:
the resulting polymers with different NMA contents was evaluated by monitoring their gel fractions and
Polymer
Thermal properties
swelling ratios after crosslinking. The equilibrium swelling behaviors of the poly(NIPAAm-co-NMA)
Heat treatment hydrogels were also investigated as a function of curing time. The results showed the hydrogels cured
Differential scanning calorimetry at shorter times or lower temperatures had lower gel fractions and higher swelling ratios. The intro-
duction of a crosslinking structure into the temperature-responsive polyNIPAAm controlled the swelling
capability and the cloud point of the crosslinked hydrogels.

1. Introduction
Poly(N-isopropylacrylamide), polyNIPAAm , is a well-known
thermally responsive polymer which contains a hydrophilic
amide (eCONHe) and a hydrophobic isopropyl group (eCH(CH3)2)
in the polymer chains. The phase separation behavior of poly-
NIPAAm aqueous solutions has been investigated in the literature
and demonstrates a lower critical solution temperature (LCST) or
cloud point at 32
C because of hydrogen bonding interactions
between the amide group and water molecules. It also exhibits
a reversible hydrationedehydration behavior with changing
temperature. PolyNIPAAm is in a swollen state when submerged in
water at a temperature lower than the LCST. The polymeresolvent
interactions are stronger than the polymerepolymer interactions.
Hydrogen bonds are bound to the hydrophilic moieties such that
the polymer is in a swollen state at temperatures lower than the
LCST and in a shrunk state at temperatures higher than the LCST [1].
Above the LCST, the polymerepolymer interactions increase due to
* Corresponding author. Department of Chemical Engineering, National Taiwan
University, No. 1, Sec. 4, Roosevelt Road, Taipei 106, Taiwan, ROC. Tel./fax: þ886 2
23623259.
E-mail address: ycchiu@ntu.edu.tw (W.-Y. Chiu).
the hydrophobic interactions making water a poor solvent for the
polymer. The polyNIPAAm chains shrink and expel water molecules
from the polymer due to the dissociation of the hydrating water
molecules from polymer. Functionality of polyNIPAAm can be
modified by introducing other functional monomers during the
synthesis. The LCST of polyNIPAAm can be adjusted by adding
either hydrophilic or hydrophobic monomers for copolymerization.
Hydrophilic co-monomers increase the LCST and the hydrophobic
co-monomers decrease it [2e5].
Crosslinked hydrophilic polymers are useful for the preparation
of networked hydrogels. Important properties, such as elastic
modulus, swelling, and permeability of crosslinked polymers
depend on degree of crosslinking, type of crosslinkers and polymer
network structure [6,7]. PolyNIPAAm and its copolymer hydrogels
have been extensively studied and utilized in various applications
such as surface sensing [8], drug delivery [9,10], separation process
[11], and immobilization. The hydrogels undergo phase transitions
when there are changes in environmental conditions such as
temperature and pH. The swelling and shrinking of the hydrogel are
diffusion-controlled such that the crosslinking degree and the
hydrogel size play important roles.
The crosslinking reactions have been performed by chelation
crosslinking [12], thermal curing [13], oxidative crosslinking, or
radiation crosslinking [14] (e.g., X-ray, UV, etc.). These reactions Table 1
have been widely used to satisfy various requirements for multi- Designation and ingredients of poly(NIPAAm-co-NMA) with different NMA
contents.
functional materials. Among these crosslinking methods, thermal
curing is the most vital method because of its convenience and Ingredient Sample
non-polluting advantages [15]. Acrylamide and aldehyde deriva- (unit: mole)
Poly(NIPAAm-co-NMA)X
tives have been well-known for crosslinking because they can X: The feeding molar percent of NMA in the copolymer
crosslink at high temperatures. The monomers, bearing these X¼5 X ¼ 10 X ¼ 15 X ¼ 20 X ¼ 30
groups and being synthesized for use in polymerization, include NMAa 0.0025 0.005 0.0075 0.01 0.015
N-methylol acrylamide (NMA), isobutoxymethylacrylamide NIPAAm 0.0475 0.045 0.0425 0.04 0.035
(IBMA), and acrylamidoglycolic acid monohydrate, etc. These APS 0.0006 0.0006 0.0006 0.0006 0.0006
functional monomers have a methylol group for thermal curing and SMBS 0.0006 0.0006 0.0006 0.0006 0.0006

a reactive double bond for polymerization. a

N-(Methylol acrylamide) (NMA) is a bifunctional monomer
containing a self-condensable methylol group and a reactive double
bond [16]. Therefore, it could be copolymerized with sodium
4-styrenesulfonate (SSNa) in aqueous phase [17] or with n-Butyl
methacrylate in emulsion polymerization [18]. The crosslinking
mechanism was proposed by Yocum and Nyquist [19] and is shown
in Scheme 1. Bis(methylene ether) would be formed by eliminating
a water molecule, and then methylene bridge would be formed by
eliminating a formaldehyde molecule in thermal curing or acid
catalyzing of NMA.
The purpose of this study is to demonstrate a new approach for
preparing thermally responsive copolymer: the thermally curable
poly(NIPAAm-co-NMA). The morphological characteristics of the
copolymer were set before thermal crosslinking, and then the
temperature was raised to carry out the crosslinking reaction.
When soaked in water, the crosslinked poly(NIPAAm-co-NMA)
retained the morphological characteristics and was still thermally
responsive. The swelling behaviors, gel fraction, and cloud point of
the copolymer were also investigated in detail.
2. Experimental
2.1. Materials
N-isopropylacrylamide (NIPAAm; Aldrich), N-Methylol acryl-
amide (NMA 48 wt%; SigmaeAldrich), ammonium persulfate (APS;
Acros), and sodium metabisulfite (SMBS; Showa) were used as
received without further purification. Distilled and deionized water
was used throughout this work.
2.2. Synthesis of poly(NIPAAm-co-NMA)
The molar composition and designation of the synthesized
copolymers are listed in Table 1. NIPAAm and NMA were dissolved
in 36 ml deionized water. APS and SMBS were dissolved in 2 ml
deionized water in separate containers. First, NIPAAm, NMA, and
deionized water were mixed in an ice bath. Second, APS(aq) was
added under stirring. After complete mixing, SMBS(aq) was then
slowly added. The SMBS and APS acted as a pair of redox initiators.
Polymerization was carried out at 0e5
C for the first 4 h and then
The concentration of NMA(aq) purchased was 48 wt% aqueous solution.
at room temperature (23
C) for another 20 h. Scheme 2 shows the
synthetic scheme of the formation of poly(NIPAAm-co-NMA).
The resulting solution was dialyzed against deionized water for
72 h to remove unreacted monomers. During this period, the
deionized water was changed every 12 h. The final dialysis product
was lyophilized by using a freeze-dryer attached to a vacuum pump
until the sample weight remained constant.
2.3. Thermal crosslinking of poly(NIPAAm-co-NMA)
The thermal crosslinking time and temperature are key factors
for NMA thermal crosslinking, so two different temperatures, 50
C
and 110
C, and six baking time conditions were applied for the post
thermal crosslinking of poly(NIPAAm-co-NMA). The copolymers
were freeze-dried and placed on the aluminum disks and baked by
using an oven at 50
C or 110
C for 0.5 h, 1 h, 2 h, 3 h, 4 h, and 5 h
separately. The post thermal crosslinking reaction is illustrated in
Scheme 3.
2.4. Characterization of poly(NIPAAm-co-NMA)
The synthesized poly(NIPAAm-co-NMA) copolymers were
analyzed using a 400 MHz 1H Nuclear magnetic resonance (NMR)
spectrometer (Bruker); the spectra were recorded in CD3OD at
room temperature.
Molecular weight distributions of the copolymer samples before
post thermal crosslinking were measured by gel permeation
chromatography (GPC) using a Waters 515 pump, Water Styragel
columns (HR1, HR3, and HR4E) at 35
C, and a Waters 2414
refractive index (RI) detector. The copolymers were freeze-dried,
and polymer solutions in THF of ca. 2 mg cm3 concentrations
were used. THF was used as the eluant at a flow rate of 1 cm3 min1.
Narrow molecular weight polystyrene standards with molecular
weights ranging from 580 to 377,400 g mol1 were used for
calibration.
2.5. Determination of cloud points
The cloud points of poly(NIPAAm-co-NMA) aqueous solutions
at a concentration of 2 wt% were measured using UV/vis spectro-
photometer (Thermospectronic) and the samples were placed in

Scheme 1. Crosslinking mechanism involved in the formation of methylene bridge of

N-methylol groups by eliminating water and formaldehyde. Scheme 2. Synthetic scheme for the formation of poly(NIPAAm-co-NMA) copolymer.
 Scheme 3. Schematic illustration of the copolymer crosslinking reaction.

the water-jacketed cell holder coupled to a temperature-controlled
circulating bath. The transmittance of visible light at 500 nm
through the hydrogel was recorded as a function of temperature.
The cloud point of poly(NIPAAm-co-NMA) solution was defined as
the temperature corresponding to a 10% reduction in the original
transmittance of the solution.
The cloud points of the thermally crosslinked copolymers were
measured by DSC. The crosslinked copolymers were wetted by
water for 24 h and were then encapsulated in DSC sample pans.
DSC thermograms were obtained using a heating rate of 5
C min1
from 10
C to 80
C using a TA Q200 System. The cloud points were
defined as the onset value of the transition-temperature chart.
2.6. Gel fraction and swelling ratio
The weights of poly(NIPAAm-co-NMA) post-curing samples
were measured and defined as Wo and the cured copolymers were
soaked in water for 2 days and the hydrogels were collected by
filtering the solution through a 300-mesh metal filter. The swollen
hydrogel weights were recorded and denoted as Ws. Then the
swollen hydrogels were dried at 110
C until their weights became
constant. The weights were recorded and denoted as Wd. The
uncrosslinked copolymer was redissolved by water. The gel fraction
was calculated using Equation (1):
W mers showed temperature-responsive behavior. The cloud point of
Gel Fraction ¼ d
Wo
And the swelling ratio was calculated using Equation (2):
Ws
Swelling Ratio ¼
Wd
Poly(NIPAAm-co-NMA) copolymers with different molar
content of NMA (10%, 20%, and 30% in feed) were cured in an oven.
The gel fraction and swelling ratio at different curing conditions
were measured. For the temperature-responsive swelling studies,
the cured copolymers were swollen at a range of temperatures over
which the cloud point transition was expected to occur.
shifts at 1.15 ppm (a) and 3.95 ppm (b) were associated with
NIPAAm (eCH(CH3)2) and NIPAAm (eCH(CH3)2), respectively. For
NMA, the chemical shift in 4.69 ppm (c) was associated with
NMA(eNHCH2eOH). Thus, we defined the actual NMA content by
equation (3). The NMA content in the polymer was similar to the
feeding composition in the cases of low NMA content. With
increasing NMA content, the actual NMA content was lower than
the feeding content.
Actual NMA content in copolymer
integration area of peak c=2
¼
Intergration area of peak b þ integration area of peak c=2
(3)
The molecular weights and molecular weight distributions of
the copolymers were characterized by GPC using THF as the mobile
phase and the results are shown in Table 2. It should be noted that
the copolymers containing 20 and 30 mol% NMA were difficult to
dissolve in THF.
3.2. The thermally responsive properties of poly(NIPAAm-co-NMA)
solutions
The aqueous solutions containing 2 wt% uncrosslinked copoly-
(1) copolymer is strongly influenced by the changes in the hydrophilic/
hydrophobic nature. Temperature-controlled UVevisible spectros-
copy was employed to detect the cloud point of the aqueous
copolymer solutions. Fig. 2 shows the transmittanceetemperature
curves. As the NMA molar content increased, the cloud point of
(2)
the poly(NIPAAm-co-NMA) copolymer shifted progressively to
higher temperatures and the transition range broadened because
the methylol group in NMA made the copolymer more hydrophilic.
The cloud points of poly(NIPAAm-co-NMA) copolymer solutions
are listed in Table 3. Higher NMA content leads to a stronger
interaction between water and the copolymers, and hence the
phase transition temperature increases.

3. Results and discussion

Table 2
The molar content of NMA in poly(NIPAAm-co-NMA) copolymer determined from
3.1. The characters of poly(NIPAAm-co-NMA) NMR analysis and the molecular weight of poly(NIPAAm-co-NMA).

Sample Feed NMA Actual NMA Molecular weight

The copolymers of NIPAAm and NMA could be easily prepared
molar content
by redox polymerization in water using APS/SMBS as initiators. The content (%)
physical properties of the NIPAAm/NMA copolymers are listed in Determined Mn Mw Mw/Mn
by NMR
Table 2. The composition of the polymers with various comonomer
PNIPAAm 0 0 11,500 20,200 1.76
contents was determined from 1H NMR spectra recorded for
Poly(NIPAAm-co-NMA)5 5 4.35 11,500 27,200 2.37
polymer solutions in CD3OD. The chemical structure of the Poly(NIPAAm-co-NMA)10 10 10.67 89,400 118,300 1.32
poly(NIPAAm-co-NMA) copolymers was characterized by 1H NMR Poly(NIPAAm-co-NMA)l5 15 13.09 81,600 104,500 1.28
spectroscopy in CD3OD (Fig. 1). The chemical shifts at Polv(NIPAAm-co-NMA)20 20 18.30 ea e e
d ¼ 1.3e2.3 ppm (d and e) were attributed to the methylene Poly(NIPAAm-co-NMA)30 30 23.95 e e e
a
protons signals (eCH2CHe) of NMA and NIPAAm. The chemical The copolymer cannot be well dissolved in THF.
 Fig. 1. NMR spectrum of poly(NIPAAm-co-NMA)30 copolymer (CD3OD; 400 MHz).
Fig. 2. Temperature dependent transmittance of poly(NIPAAm-co-NMA) solution,
NMA molar content ¼ 5, 10, 15, 20, and 30.
3.3. Thermal crosslinking
In order to prevent excessive solubility in water, the copolymers
were crosslinked by thermal curing. NMA performed the thermal
crosslinking function in poly(NIPAAm-co-NMA) which led to the
formation of bis(methylene ether), and a methylene bridge is
formed by consuming water and formaldehyde molecules, as
shown in Scheme 3.
Fig. 3 shows the effect of NMA molar content on the gel fraction
of copolymer, where the gel fraction at a curing temperature of
50
C is plotted against curing time. Poly(NIPAAm-co-NMA)10,
poly(NIPAAm-co-NMA)20, and poly(NIPAAm-co-NMA)30 took
5 h, 3 h, and 2 h respectively, to reach 70% gel fraction. The gel
fraction increased as the crosslinking degree increased and a higher
concentration of NMA led to a higher crosslinking reaction rate.
Fig. 4 shows the gel fraction of copolymers cured at 110
C. The gel
fractions of poly(NIPAAm-co-NMA) containing 10, 20 and 30 mol%
of NMA, which were cured for 30 min, were 43.1, 72.2%, and 87.7%,
respectively. All of the copolymers reached 90% gel fraction after
Table 3
The cloud point of poly(NIPAAm-co-NMA) without thermal curing.
Sample Cloud point (
C)
Detected by UVevis
PolyNIPAAm 32.1
Poly(NIPAAm-co-NMA)5 35.0
Poly(NIPAAm-co-NMA)10 36.5
Poly(NIPAAm-co-NMA)15 38.9
Poly(NIPAAm-co-NMA)20 42.1
Poly(NIPAAm-co-NMA)30 48.0
one hour thermal curing. Figs. 3 and 4 show that the crosslinking
rate could be significantly increased at higher temperatures and
higher NMA contents.
3.4. Swelling ratio of poly(NIPAAm-co-NMA)
Cured poly(NIPAAm-co-NMA) copolymers were soaked in water
for 2 days, and the swelling ratio was calculated using equation (2).
The swelling behavior was studied for poly(NIPAAm-co-NMA)
hydrogel with different NMA ratio and at various curing times at
50
C or 110
C. Fig. 5 shows the swelling ratios of copolymer cured
at 50
C are plotted against the curing time. The swelling ratio of
poly(NIPAAm-co-NMA)10 decreased with higher curing times,
consistent with a higher degree of crosslinking. The swelling ratios
of poly(NIPAAm-co-NMA) with 10, 20, and 30 mol% NMA with 1 h
curing time were 59.8, 45.0, and 35.2 respectively. The higher NMA
molar content of the copolymers rendered the hydrogels highly
crosslinked and less water-absorptive.
The swelling ratios of the copolymer cured at 110
C are plotted
against the curing time, and are shown in Fig. 6. For the copolymer
hydrogels at a curing time of 1 h, the swelling ratio of
poly(NIPAAm-co-NMA)10 was significantly larger than those of
poly(NIPAAm-co-NMA) 20 and 30. When the curing time was
higher than 3 h, the swelling ratios of the three copolymers were
around 10. Two factors contributed to the swelling ratio of the
copolymer. One is the crosslinking degree of the copolymer, and the
other is the content of uncured NMA. In the thermal curing process,
the NMA in the copolymer chains formed new crosslinking sites.
When the NMA content increased, the copolymer hydrogels were
more strongly crosslinked with more NMA crosslinking sites,
resulting in a higher degree of crosslinking. However, the fraction of
Fig. 3. Gel fraction of poly(NIPAAm-co-NMA) cured at 50
C.

Fig. 4. Gel fraction of poly(NIPAAm-co-NMA) cured at 110
C.
Fig. 5. Swelling ratio of poly(NIPAAm-co-NMA) cured at 50
C.
uncured NMA also increased significantly due to the steric
hindrance of the crosslinked chains of the copolymers. These two
factors influenced the swelling ratio of copolymer in an opposite
way. It explained the results that the swelling ratios of
poly(NIPAAm-co-NMA)10, 20, and 30 were about the same when
the curing time was higher than 3 h.
Fig. 6. Swelling ratio of poly(NIPAAm-co-NMA) cured at 110
C.
Fig. 7. Swelling ratios of poly(NIPAAm-co-NMA) hydrogels with different NMA
contents as a function of soaking temperature. The copolymers were cured at 50
C for
5 h.
The temperature dependence of the equilibrium swelling ratio in
water of the poly(NIPAAm-co-NMA) copolymer with varying
amounts of NMA cured for 5 h at 50
C and 110
C, is depicted in
Figs. 7 and 8 respectively, With the soaking temperatures in the
range of 25e65
C. The data show that all poly(NIPAAm-co-NMA)
copolymers, regardless of the amount of the NMA, had similar
swelling behaviors as a function of temperature. All poly(NIPPAm-
co-NMA) copolymers exhibited a swollen state at lower tempera-
ture, and a shrunk state at higher temperatures. Poly(NIPAAm-co-
NMA) copolymers showed stable swelling ratios at lower tempera-
tures, but they expelled water from the copolymers at high
temperatures, which is attributed to the aggregation of the copol-
ymer chains. The swelling ratios of cured poly(NIPAAm-co-NMA)10
copolymer were 41.9 at 25
C and 4.0 at 65
C, respectively. The
relative swelling performance index between 25
C and 65
C
(defined as the ratio of the two ratios, 41.9 and 4.0) was 10.47. With
increasing NMA content, the relative swelling performance indices
for poly(NIPAAm-co-NMA)20 and poly(NIPAAm-co-NMA)30 drop-
ped to 2.96 and 1.75, respectively. A higher NMA content led to lower
temperature sensitivity when the samples were cured at 50
C for
5 h. It is believed that the increase of crosslinking degree will reduce
the average chain length between crosslinking points which in turn
leads to the reductions of volume expansion and water absorption at
swelling. Fig. 8 shows similar low swelling ratio at each soaking
temperature. This is attributed to a high degree of crosslinking
during 5 h, 110
C curing.
Fig. 8. Swelling ratios of poly(NIPAAm-co-NMA) hydrogels with different NMA
contents as a function of soaking temperature. The copolymers were cured at 110
C
for 5 h.
 Fig. 9. DSC thermograms of poly(NIPAAm-co-NMA)10 copolymers soaked in water which were cured at 50
C for 0, 1, 3, 5 h.
Fig. 10. Photographs of poly(NIPAAm-co-NMA)10 copolymers soaked in water: (a) uncured, soaked at 23
C, (b) uncured, soaked at 50
C, (c) cured at 50
C for 5 h, soaked at 23
C
and (d) cured at 50
C for 5 h, soaked at 50
C.
Fig. 9 shows the DSC thermograms of poly(NIPAAm-co-NMA)10:
uncured, and cured for 1, 3, and 5 h, respectively. The cloud point of
the copolymer hydrogel was defined as the onset of the transition in
the thermogram. The cloud points of poly(NIPAAm-co-NMA)10
uncured, cured for 1, 3 and 5 h were 38.93
C, 38.15
C, 36.46
C,
and 35.96
C, respectively. The introduction of crosslinking
increased the polymerepolymer interaction. With increasing curing
time, the cloud point shifted to lower temperatures and the transi-
tion range was broadened due to the increasing crosslinking density.
The photographs of the uncured poly(NIPAAm-co-NMA)10 and
cured at 50
C for 5 h in water are shown in Fig. 10. When the
soaking temperature was 23
C, the uncured sample was in
a transparent state, dissolved in the deionized water (Fig. 10a). The
cured sample was a transparent hydrogel (Fig. 10c). At 50
C, higher
than the cloud point, the uncured sample transformed into a milky
white dispersion (Fig. 10b). The cured poly(NIPAAm-co-NMA)10
was also thermally responsive, but a distinct milky white hydro-
gel was formed in a separate phase (Fig. 10d). The formation of
hydrogel in the cured sample indicated that copolymers were
crosslinked after post-curing and the hydrogel of poly(NIPAAm-co-
NMA)10 remained thermal responsive properties.
4. Conclusions
In this work, NIPAAm and NMA were copolymerized by redox
polymerization to form thermally curable poly(NIPAAm-co-NMA)
copolymers. The cloud point of the copolymers shifted to higher
temperatures with increasing NMA molar content. These
copolymers could be converted into crosslinked gel networks by
a thermal curing process after their synthesis. The cloud point was
only slightly influenced by the crosslinking degree. The investigation
of the thermally cured poly(NIPAAm-co-NMA) hydrogels showed
that a higher NMA content, a higher curing temperature and a longer
curing time led to an increase in the gel fraction. The swelling ratio of
poly(NIPAAm-co-NMA) hydrogels was strongly dependent on NMA
molar content, curing time and curing temperature.
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