Radiation Physics and Chemistry 60 (2001) 625628

Solvent eect on grafting polymerization of NIPAAm onto

cotton cellulose via g-preirradiation method
Lu Jun, Li Jun, Yi Min*, Ha Hongfei
Department of Technical Physics, Peking University, Beijing 100871, Peoples Republic of China
Received 10 July 2000; accepted 10 September 2000

Abstract
Grafting polymerization of N-isopropylacrylamide (NIPAAm) onto cotton cellulose preirradiated in air by 60Co-grays was accomplished in mixed solvents of water and alcohols or acetone. The grafting yields changed with dierent
ratios of water and organic solvents. In the system of solvents comprised of water and methanol, the Trommsdor eect
appeared in the curve of the grafting yields vs. the concentrations of the monomer. In the same system, the dependence
of the grafting yield of NIPAAm on the grafting temperature was dierent from that of acrylamide (AAm). The relation
between the grafting yields of the samples and their crystallinities measured by X-ray diraction could be regarded as a
proof of the third-phase conception. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Cotton cellulose; N-isopropylacrylamide; Preirradiation grafting polymerization; Trommsdor eect; Third phases

1. Introduction
Cotton cellulose is a kind of natural polymer of
common use. Due to its advantages, it cannot be entirely
substituted by articial bers now. However, cotton
cellulose itself has some defects which limit its usage.
The pursuits to modify cotton cellulose and its
derivatives have chronically been carried out and
grafting polymerization is one of the important methods. Hence, grafting initiated by g-irradiation, extensive
attention has been paid because of its specic merits
(Zanhran et al., 1980; Nakamura et al., 1972; Sagu and
Bhattacharyya, 1986; Ghosh et al., 1983; Wu et al.,
1992; Chye Ang et al., 1982; Sakurada et al., 1964; Dilli
and Garnett, 1967, 1968, 1970; Dilli et al., 1972).
NIPAAm is one of the monomers that have appealed
to a great deal of investigation in the recent twenty
years. Its homopolymer PNIPAAm possesses temperature sensitivity and can act as a functional polymer with
great potential. It is conceived that grafting NIPAAm
onto cotton cellulose achieves some modication results.
*Corresponding author.
E-mail address: ymin920@ibmstone.pku.edu.cn (Y. Min).

Grafting NIPAAm onto preirradiated cotton can not

only explore on modication but also provide certain
information to the mechanism of the grafting polymerization on cotton cellulose via g-preirradiation. Our
previous research in the preirradiation grafting of
NIPAAm on cotton cellulose in pure water systems
indicated a special temperature eect on such grafting
reactions and the important role of interphases between
crystal and amorphous regions of cellulose molecules
(Liu et al., 1999). Current research using mixed solvents
of water and organic solvents such as alcohols during
grafting reactions probed still further into such idea.

2. Experimental
2.1. Materials
The ordinary cotton cloth, obtained from a commercial source, was rst extracted with ethanol in the
Soxhlet apparatus for 5 h and then immersed in the
solution of 1% NaOH and boiled for 3 h. Afterwards, it
was washed with distilled water to neutral. Finally, the
cotton was dried in the vacuum oven at 408C overnight

0969-806X/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
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L. Jun et al. / Radiation Physics and Chemistry 60 (2001) 625628

and then stored in the desiccator. The solutions for the

grafting reactions were prepared by mixing tri-distilled
water with organic solvents which were AR or GR
degree.
2.2. Methods
The treated cotton was cut into small pieces of about
0.1 g and weighed. The samples were put in the tube and
irradiated in air with the dose rate of 374 Gy/min for
90 min by 60Co-g source. The total dose was 33 kGy,
because according to the former work of our lab such
dose reached the platform region of variation of the
grafting yield (Liu et al., 1999). The irradiated samples
were soaked in the solution of the monomer NIPAAm
which was already deoxygenated by N2 for about 0.5 h.
Under certain temperature controlled by a water bath,
the reaction lasted for 4 h with N2 aeration. The cotton
pieces were taken out and extracted with ethanol in the
Soxhlet extractor for about 12 h to remove the homopolymer of the monomer. Then they were dried in the
vacuum oven and weighed again. The grafting yield
(GY%) was nally calculated according to the following
formula:
GY%

Fig. 1. The eect of solvent comprising methanol (&), acetone

(*), ethanol (*), propanol (^), or isopropanol (m) on the
grafting yield of 6% NIPAAM at 218C.

W  W0
100%:
W0

3. Results and discussion

3.1. Eect of the composition of the solvents on the
grafting yield
In the mixed solvent of water and methanol, the
grafting yield rst increased with the augment of
the percent of the methanol in the solvent until the
ratio of water:methanol was 4 : 1. Then it began to
decrease to almost zero in pure methanol. (In the
following experiments the mixed solvents of 20%
methanol were chosen.)
However, in the systems of water and other organic
solvents, such as ethanol, propanol, isopropanol and
acetone, the grafting yields decreased continuously from
pure water to pure organic solvents, where the grafting
yields were all almost zero. From Fig. 1, it could be
concluded that alcohols had inhibiting eects of
dierent degrees on grafting of NIPAAm, while acetone
was inert.
In the double logarithmic diagram of grafting yields
vs. contents of the mixed solvents (Fig. 2), linear
relationships within certain range of the solvent contents
were obtained. Moreover, the relative magnitudes of the
slopes of these three tted lines (Table 1) may have
certain relation with the chain transfer constants of
those three solvents used.

Fig. 2. The logarithm of the grafting yield vs. the logarithm of

the percent of ethanol (&), propanol (*), or isopropanol (m) in
the mixed solvent.

Table 1
The absolute value of slope of tted line
Organic solvent

Absolute value of slope

Ethanol
Propanol
Isopropanol

0.99
0.98
1.36

The alcohols are good swelling (or wetting) agents for

cotton cellulose. During grafting reactions they can help
monomers approach the active sites in cellulose molecules more easily and promote reactions. On the other
hand, they are relatively eective chain transfer agents
which could decrease the grafting yields (Lawrence and
Verdin, 1973). The two opposite roles of these organic
agents took eect simultaneously in the mixed solvents
of water and the organic agents. As to the methanol,

L. Jun et al. / Radiation Physics and Chemistry 60 (2001) 625628

because of its relatively small molecular size which

contributes to its strong swelling capacity and its
relatively weak chain transfer capacity, it improves
grafting polymerization when its concentration in the
mixed solvent with water is low. When its concentration
increases, its chain transfer role gradually surpasses its
swelling role and consequently it aects the grafting
yield adversely (Fig. 1). As far as ethanol, propanol and
isopropanol are concerned, their molecular sizes are
relatively large and have relatively weak swelling
abilities. Their chain transfer abilities which are
relatively strong exceed their swelling abilities within
the whole content range of mixed solvents, so grafting
yields decrease continuously.
Garnett and co-workers have investigated comprehensively on the grafting polymerization on cellulose
through direct irradiation (Dilli and Garnett, 1967,
1968, 1970; Dilli et al., 1972). In his work of additives
eects, Garnett also used alcohols as solvents (Dilli and
Garnett, 1967, 1968; Dilli et al., 1972). Under appropriate conditions Garnett gained quite ne grafting
yields in solvents of pure alcohols, which was apparently
dierent from our results of preirradiation grafting.
Though the alcohols also have chain transfer roles in
direct irradiation grafting, the high utilizing ratio of free
radicals may eectively compensate the adverse roles of
alcohols and thus make their swelling roles predominant. Moreover, in direct irradiation grafting the main
chain transfer reaction is dierent from that in
preirradiation grafting and inuences the grafting
reaction much less (Dilli and Garnett, 1970).

3.2. Eect of the concentration of NIPAAm on the

grafting yield
Our team has investigated on the relationship of the
grafting yield and the NIPAAm concentration in the
preirradiation grafting of NIPAAm on cotton cellulose
in pure water systems (Liu et al., 1999). Because the
solubility of NIPAAm in water was limited, the former
experiments were performed within the concentration
range from 0 to 10% NIPAAm. However, in the mixed
solvents of water and alcohols, the solubility of
NIPAAm could be much greater. Meanwhile, the
comparison of the results in pure water and those in
mixed solvents could help to investigate on the mechanism of grafting polymerization. In the current experiments, the ratio of water and MeOH in the mixed
solvents was 4 : 1 (v : v).
In Fig. 3, along with the augment of the concentration
of NIPAAm, the main trend of the grafting yield was to
increase. The two peaks around 15 (g : v) and 40% were
probably due to the Trommsdor eect. The small peak
around 15% might be attributed to water, while the
large one around 40% to methanol.

627

Fig. 3. The eect of NIPAAm concentration on the grafting

yield in the solvent of 4 : 1 (v : v) water/methanol at 218C.

Fig. 4. The eect of the grafting temperature on the grafting

yield of 6% NIPAAm (&) or Aam (*) in the solvent of 4 : 1
(v : v) water/methanol.

3.3. Eect of the grafting temperature on the grafting

yield
In Fig. 4, the grafting yield of AAm onto the cotton
decreased continuously along with the increase of the
grafting temperature, while that of NIPAAm increased
rst till 40oC and then fell down. In pure water systems,
the grafting yield of NIPAAm on the cotton cellulose
continuously went up with the increasing grafting
temperature, while that of AAm fell down continuously
(Liu et al., 1999).
The grafting temperature may have such inuences on
the grafting reaction as the following. (1) Higher
temperature causes quicker decay of trapped free
radicals. (2) When the temperature ascend to a certain
level, the peroxides (or hydrogen peroxides) decompose
and participate in initiating the grafting reaction. (3)
Higher temperature causes faster diusion of monomer
molecules to the matrix. (4) Higher temperature causes
higher grafting rate. Among the above inuences, the
rst one is of the adverse eect for the grafting yield

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L. Jun et al. / Radiation Physics and Chemistry 60 (2001) 625628

diraction (Cu target, 40 kV, 100 mA) showed that when

the grafting yield of the grafted product is high, its
crystallinity is low. The result supported the theory of
the third phaseto a certain extent (Fig. 5).

References

Fig. 5. The eect of the grafting yield on crystallinity of the

grafted product.

while the rest three are of improving aects. For AAm

the grafting polymerization is typically induced by
trapped radicals. The adverse eect surpasses the
improving eects, so the grafting yield tends to decrease.
But for NIPAAm, there is something special.
PNIPAAm has temperature sensitivity and its LCST is
within 30408C (Liu et al., 1999). From 21 to about
408C, the increase of the temperature leads to the
shrinking of PNIPAAm which immobilizes the homopolymer and hence inhibits the termination reaction.
Consequently, the grafting yield increases within this
range.
3.4. Discussion on the third phase
In a previous work on preirradiation grafting of
temperature sensitive hydrogel on cotton cellulose
fabric, a concept concerning third phase was put
forward (Liu et al., 1999). The present study led us to
believe the experimental results t well the third phase
concept. The trapped radicals in the crystalline region of
the preirradiated cellulose could not contribute to
grafting of NIPAAm because the solvent could not
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reported before. In addition, the trapped radicals in the
interphase could be complemented continuously by
migration from the crystalline regions.
If that is the point, the crystallinity of the sample
should decrease after grafting. Measurement of X-ray

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