Colloid & Polymer Science Golloid & Polymer Sci 262:677-682 (1984)

POLYMER SCIENCE

Aqueous polymerization of methacrylamide initiated

by potassiumpersulfate-L-cystein hydrochloride redox system
K. Behari and K. C. Gupta

Chemical Laboratory, University of Allahabad, India

Abstract:The aqueous polymerizationof methacrylamideinitiatedby potassiumpersul-

fate-L-cysteinhydrochlorideredox systemhas been studied at 35 + 0.01~ under nitro-
gen atmosphere. The initialrate of polymerizationhas been found to be directllypropor-
tional to the monomer and activatorconcentration, in the range of 1.0 x 10- to 4.0 x
10-I moi dm-3 and 1.25 x 10-~ to 5.0 x 10-~ tool dm-3 respectively.The order with
respect to initiatorhas been found to be 0.5, indicatingthereby that the terminationtakes
placeby bimolecularprocess. The overallenergyof activationhas been found to be 53 _+1
KJ/mol.
Key words:Kinetics,methacrylamide,reaction scheme, viscosity,additives.

Introduction Viscosity Measurements

The peroxydisulfate ion in the presence of different The polymethacrylamidesamples were dissolvedin water and
the viscosityat differentconcentrationshas been measuredby using
reducing agents has been used for aqueous polymer- an Ubbelohde viscometerat 30 _+0.01 ~ to determinethe intrinsic
ization of acrylamide [1-4], methacrylamide [5-7], viscosity.
acrylonitrile [8-9], and methylmethacrylate [10]. The
peroxydisulfate ion itself was also used successfully as
an initiator for the polymerization of acrylamide [11]. Results and Discussion
Japanese workers [12,13] have reported that the
In the aqueous polymerization of methacrylamide
amount of cystein present in the wool is responsible for
initiated by potassiumpersulfate L-cystein hydrochlo-
the grafting of methylmethacrylate with persulfate
ride, the following reaction scheme can be proposed.
catalyst. This has prompted us to employ L-cystein
hydrochloride as an activator in the polymerization of
2 H S C H e C H ( C O O H ) N H 2 +K2S208 k ,
methacrylamide in the presence of peroxydisulfate fast
ion.
2SCH2CH(COOH)NH 2+2KHSO4 (1)

Initiation
Experimental
S C H 2 C H ( C O O H ) N H 2+ M k~ , J ~ l (2)
Methacrylamide (Fluka, A.G.) was purified by recrystallization
from benzene-ethanoland dried under vacuum for about 12 hours
over silica gel. Potassiumpersulfate(E. Merck) was recrystallized Propagation
twice from distiliedwater. L-Cysteinhydrochloride and other rea-
gents used were of (B. D. H.) A. R. Grade. All the solutionswere MI + M kp , M2
prepared using twice distilledwater obtained by distillationin the
presence of alkaline potassiumpermanganate.Nitrogen gas was )VIn_I+ M kp ~ IVI n (3)
purified by passingthrough Fieser's reagent, pyragallol,KOH and
conc. I~I2SO 4 solutions.The apparatus used was a modifiedform of Termination
that of Baxendale[14]. The kineticsof polymerizationhas been fol-
lowed as reported elsewhere [15]. (4)
K 764
678 Colloid and Polymer Science, VoL 262 9No. 9 (1984)

It has been observed that the reaction proceeds
without induction period. The growing chain radicals
as shown in step (4) undergo a bimolecular termina-
tion. The rate expression has been derived.applying
a steady state condition for the radical [SCH2.CH
(COOH)NH2] and the growing chain radicals (Mn).
[SCH2CH(COOH)NH2] =
k [K2S208] [HSCH2CH(COOH)NH2] 2
k,[M]
[M~] = (k~[M] [SCH2CH(COOH)NH2] I v2
2kt
Assuming the rate constants for all the propagation
steps to be the same, the rate of polymerization can be
given as
Rp = kp [M] [_/V/~]
Dependence of rate on initiator concentration
The effect of initiator concentration variation (table
1) reveals that on increasing the concentration of initia-
tor the initial and maximum conversion increases at a
constant concentration ofmethacrylamide and cystein
hydrochloride. It is evident from equation (5) that on
increasing the concentration of initiator, the stationary
concentration of radicals increases, hence the initial
rate and maximum conversion has been found to
(5) increase.
The order with respect to initiator has been calculat-
ed from the logarithmic plot of Rii. e., percent conver-
sion per minute at 10 minutes vs initial concentrations
] (6) of initiator (fig. 1), and has been found to be 0.5, clearly
indicating a bimolecular mode of termination.
The intrinsic viscosity of the polymethacrylamide
decreases on increasing the concentration of initiator
(fig. 2). Similar results have been given by Palit et al.
[16].
(7)

by putting the values from equation (5) and (6) in the

equation, the rate expression is as follows.

ap = kl/2[M] [K2S208]'/2[HSCH2CH(COOH)NH2] (8)

On the basis of the above scheme the kinetic chain

length can be given as

v = -(2k kt) 1/2 [K2S2L)sj kp [M]

~ 7l/2 [HSCH2CH(COOH)NH2] (9)

It is evident from the above equation (9) that the ki-

netic chain length is proportional to [M], [K2S208] 1/2
and [HSCH2CH(COOH)NH2] -1.

Table 1. Dependence of rate on persulfate concentration

[K2S208] Percent conversion at different intervals of time (rain) [r/] 102

10 4 mol d m -3 5 15 30 45 75 120 dl/g

3.1 1.38 5.50 11.25 14.50 17.63 19.00 6.84

4.0 1.75 7.56 12.88 15.63 18.50 20.25 5.78
5.0 2.04 8.50 14.13 16.88 19.63 21.25 5.47
6.6 2.25 9.06 15.13 18.38 21.38 22.78 4.63
10.0 2.80 11.82 17.50 20.12 22.75 22.76 3.54

[Methacrylamide] = 2.0 x 10-1 tool d m -~, [L-cystein hydrochloride] = 2.0 x 10-3 mol d m -3
Behari and Gupta Aqueus pymerizatin f methacryamide initiated by ptassiumpersufate-L-cystein hydrchride redx system 679

0.8 1.2

I
fi.-
0.8
0.71
~ 9 5
o
% 0.4'
.-0.6
0.0 I I I I
D~
0
0,09 0.29 0.49 0,69 0.89
+
0.50'

Fig. 3. Temp. 35 ~ Double logarithmic plot of initial rate of poly-

I merization (Ri) vs concentrations of cystein hydrochloride.
0.40 i i i J
0,50 0.60 0.70 0.80 0.90 1.00 [K2S208] = 5.0 x 10_4 mol. dm -3, [Methacrylamide] =2.0 x 10-1
tool. dm -3
4+ log(l] niti at or..]/ mo I d m-'}

Fig. 1. Temp. 35 ~ Double logarithmic plot of initial rate of poly- Dependence of rate on activator concentration
merization (Ri) vs concentrations of persulfate. [Methacrylamide]
= 2.0 x 10-~ mol. dm -3, [L-cystein hydrochloride] = 2.0 x 10-~ The results obtained on varying the concentration
mol. dm -3 of L-cystein hydrochloride are given in table 2. It
clearly indicates that the rate increases up to a certain
limit of activator concentration and thereafter the
maximum conversion and initial rate of polymeriza-
tion decreases. Such a trend has earlier been reported
in serveral other redox initiated polymerizations
[3, 17].
30 The order with respect to cystein hydrochloride
(1.25 x 10-3--5.0 10-3moldm-3)hasbeenfoundto
be close to unity (fig. 3). However, the activator
T20 exponent was found to deviate from unity on higher
concentrations of cystein hydrochloride which might
be due to a combination reaction of primary free radi-
cals.

I I I SCH2CH(COOH)NH2 + SCH2CH(COOH)NH2
1.0 2.0 3.0 3.5
10~ff[Init iot0r]/tool dr-63 1. NH2(COOH)CHCH2-S-S-CH2-CH(
COOH)NH2
Fig. 2. Temp. 35 ~ Variation of the reciprocal of the intrinsic vis- A similar explanation has been given by Shukla et al.
cosity at 30 + 0.01 ~ with the square root of the potassium persul-
fate concentrations. [Methacrylamide] = 2.0 x 10-I tool. dm -3, [L- [18]. The intrinsic viscosity decreases on increasing
cystein hydrochloride] = 2.0 10-~ tool. dm -3 the concentration of activator.

Table 2. Dependence of rate on L-cystein hydrochloride concentration

[L-cystein- Percent conversion at different intervals of time (min) [r/] x 102

hydrochloride]
x 103 mol dm -3 5 15 25 50 75 100 dl/g

1.25 1.06 4.66 8.73 15.84 19.16 20.33 5.70

1.67 1.73 6.50 11.83 18.40 21.32 21.66 5.55
2.50 2.16 10.50 16.17 21.33 22.84 23.30 5.10
3.33 2.50 12.30 18.36 24.28 26.34 27.28 4.16
5.00 3.63 16.66 20.66 24.00 25.00 25.32 3.45

[Methacrylamide] = 2.0 x 10-1 mol dm -3, [K'2S208] = 5.0 X 10 - 4 mol dm -~

 680 Colloid and Polymer Science, Vol. 262. No. 9 (1984)

0.9 0 1.2

I 0.7
l o.9~- ~ x l O = , 3
ai-
h= o
-.1
~ 0.5 +
+ ~0.3-

0.3 ~ ~ i I
0.0 0.2 0.4 0.6 I
3.09 3,18
I
3.30 3,38
I

l+tog[[l,lonomer]/moidr~3}
Fig. 4. Temp. 35 ~ Double logarithmic plot of rate of polymeriza-
tion (Rp) vs concentrations of methacrylamide. [KzS2Os] = 5.0
10-4 tool. dm -3, [L-cystein hydrochloride] = 2.0 x 10_3 mol. dm -3
Fig. 5. Arrhenius plot of initial rate of polymerization (Ri) vs recip-
rocal of absolute temperature (T) of polymerization, [Methacryl-
amide] = 2.0 x 10-1 tool dm -3 [K2S208] = 5.0 x 10-4 mol. d m -3,
[L-cystein hydrochloride] = 2,0 x 10-3 tool. dm -3

Dependence of rate on monomer concentration
The initial rate and maximum conversion increases
with increasing monomer concentration (1.0 x 10-i _
4.0 10 -1 mol dm -3 in table 3). The monomer expon-
ent has been found to be close to unity (fig. 4). The
deviation in the monomer exponent at a higher con-
centration of monomer can be explained in terms of a
cage effect i. e., at higher concentrations of monomer
the free radicals are imprisoned in a solvent cage,
which reduces the total concentration of active radi-
cals, hence the rate of polymerization decreases as sug-
gested by Rigg et al. [19]. Similar results have been
reported by Burfield et al. [20], in the peroxydisulfate
ion initiated polymerization of methacrylamide. The
intrinsic viscosity increases linearly up to 2.0 x 10 -1
mol dm -3 concentration of monomer, thereafter the
steady increase in intrinsic viscosity is not maintained.
Temperature effect
The rate of polymerization and maximum conver-
sion increases on increasing the temperature from 20 ~
to 40 ~ and any further increase in temperature causes
a retarding effect on the rate as well as on maximum
conversion (table 4). At a higher temperature the rate
of termination by bimolecular interaction is faster than
the propagation. The overall energy of activation has
been calculated from the Arrhenius plot (fig. 5) and has
been found to be 53 _+ 1 KJ/mole. From the results
given in table 4, it is clear that the intrinsic viscosity
decreases on increasing the temperature, thereby it
reveals that the degree of polymerization decreases at a
higher temperature.
Effect of additives
The effect of inorganic salts MnSO4 94H20; KCL
and Na2C204 have been studied. Figure 6 clearly
reveals that initial rate of polymerization as well as
maximum yield decreases in the presence of KC1
which is due to the increase in ionic strength of the
medium. Similarly in the presence of sodium oxalate,
the initial rate of polymerization as well as maximum
yield decreases which is due to the production of oxa-

Table 3. Dependence of rate on methacrylamide concentration

[Metha Percent conversion at differentintervals o f t i m e ( m i n ) [r/] x 102

crylamide]
x 10 mol dm -3 5 10 20 35 50 60 70 90 dl/g

1.0 0.80 1.90 4.20 7.60 10.35 11.55 12.05 13.30 2.45
1.33 1.20 2.52 5.60 9.95 13.06 13.85 14.62 15.40 3.25
1.60 1.52 3.10 6.90 12.48 14.52 15.82 17.10 18.06 3.92
2.0 1.77 3.70 8.13 14.18 17.85 19.02 19.75 20.52 5.12
4.0 2.85 7.15 12.30 15.70 17.04 17.80 18.40 18.80 6.68

[K2S208] = 5.0 x 10_4 mol dm -3, [L-cystein hydrochloride] = 2.0 x 10-3 mol dm -3
Behari and Gupta queus pyrnerizatin of methacryamide initiated by ptassiurnpersufate-L-ystein hydrchride redox system 681

Table 4. Temperature effect

Temperature Percent conversion at different intervals of time (min) [7] x 102

~ 5 15 35 50 75 95 dl/g

25 0.84 4.00 12.02 15.83 17.60 17.82 7.28

30 1.02 5.66 14.34 17.66 18.67 19.16 6.52
35 1.33 8.16 16.84 19.30 20.34 20.67 5.42
40 1.70 11.34 18.83 21.00 21.67 22.00 4.12
45 2.50 13.34 19.38 20.16 21.00 21.18 3.92
50 2.16 9.82 15.50 20.33 19.50 19.93 2.22

[Methacrylamide] = 2.0 x 10-3 mol d m -3, [K2S2Os] = 5.0 x 10 -4 tool. d m -3, [L-cystein hydrochloride] = 2.0 x 10-3 mol d m -3

26
M n S O 4 4- H ~
contrary to the results of other workers [21]. This
might be due to the fact that fluoride ions may not
20
.o/ ~ --o Additi,,~ allow the growing chains to come closer to participate
in mutual termination. The manganous sulfate has also
shown extraordinary behaviour, i.e., by addition of
manganous sulfate, the initial rate and maximum con-

i,, lo
Lo,, version increases in the present redox system, which
may be due to the oxidation of Mn (II) by persulphate
to Mn (III). The manganese (III) abstracts hydrogen
atom from the organic substrate to produce the free
radicals [22].
~ 5 The anionic detergents like sodium oleate and
sodiumlauryl sulfate above their CMC values, increase
the initial rate of polymerization and maximum yield
0 I I I I
30 60 90 120 but the cationic detergent cetyltrimethylammonium
Time (rnin) ) bromide decrease the rate effectively as reported by
Fig. 6. Effect of additives. [Methacrylamide] = 2.0 x 10-1 mol other workers [16], (table 5).
d m -3, [Potassiumpersulfate] = 5.0 x 10-4 mol d m -3, [L-cystein The water miscible organic solvents like methanol,
hydrochloride] = 2.0 x 10-~ tool d m -3. [Additives] = 1.0 x 10-2 ethanol and propanol were found to be rate depress-
mol d m -3
ing agents, which is due to the fact that these solvents
decrease the area of shielding of a strong hydration lay-
late radicals which actively participate in the termina- er in aqueous medium resulting in the termination of
tion of growing polymer chains and primary free radi- the growing chains. They also decrease the inter-chain
cals. The complexing agent, sodium fluoride, has hydrogen bonding between polymer chains, therefore
shown a peculiar result in this sysem, i. e. it enhances the tendency of mutual termination of the polymer
the initial rate and decreases the maximum conversion, chains increases (table 6).

Table 5. Effect of detergents

Percent conversion at different intervals of time (min)

Detergents
10 20 40 60 80 120

Blank 4.17 12.50 17.50 19.75 21.00 21.62

[Sodiumoleate] = 8.0 x 10-4 mol d m -3 8.62 14.25 18.84 21.30 22.52 23.75
[Sodiumlaurylsuphate] = 8.0 x 10-3 tool d m -3 15.45 18.82 21.05 22.62 23.40 24.12
[CTAB] = 2.0 x 10-3 mol d m -3 1.62 3.62 8.50 12.12 14.50 16.12

[Methacry!amide] = 2.0 x 10-3 mol d m -3, [K2S208] = 5.0 x 10-4 mol d m -3, [L-cystein hydrochloride] = 2.0 x 10-3 mol d m -3
682 Colloid and Polymer Science, VoL 262 9No. 9 (1984)

Table 6. Effect of water miscible organic solvents

[Alcohols] Percent conversion at different intervals of time (min)

5 % v/v 10 20 40 60 80 120

Blank 4.17 12.50 17.50 19.75 21.00 21.62

Methanol 3.62 9.76 16.12 18.87 20.12 20.95
Ethanol 2.74 6.87 13.80 16.55 17.95 18.37
Propanol 1.95 4.37 9.86 13.52 15.51 17.70

[Methacrylamide] = 2.0 x 10-1 mol dm -3, [K2S2Os] = 5.0 10-4 mol dm -3, [L-cystein hydrochloride] = 2.0 x 10-3 mol dm -3

Acknowledgement 12. Arai K, Nigeshi M, Ichikova R, Okoida S (1967) Sen i Gak-

One of the authors, K. C. Gupta, is thankfull to C. S. I. R. New
Delhi for the award of a senior research fellowship.
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Received december 5, 1983;
recived and accepted march 19, 1984
Authors' address:
K. Behari
Chemical Laboratory
University of Mlahabad
Allahabad-211002, India