POLYMER SCIENCE
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 Dependence of rate on initiator concentration
without induction period. The growing chain radicals
The effect of initiator concentration variation (table
as shown in step (4) undergo a bimolecular termina-
1) reveals that on increasing the concentration of initia-
tion. The rate expression has been derived.applying
tor the initial and maximum conversion increases at a
a steady state condition for the radical [SCH2.CH
constant concentration ofmethacrylamide and cystein
(COOH)NH2] and the growing chain radicals (Mn).
hydrochloride. It is evident from equation (5) that on
increasing the concentration of initiator, the stationary
[SCH2CH(COOH)NH2] =
concentration of radicals increases, hence the initial
rate and maximum conversion has been found to
k [K2S208] [HSCH2CH(COOH)NH2] 2
k,[M] (5) increase.
The order with respect to initiator has been calculat-
ed from the logarithmic plot of Rii. e., percent conver-
[M~] = (k~[M] [SCH2CH(COOH)NH2] I v2 sion per minute at 10 minutes vs initial concentrations
2kt ] (6) of initiator (fig. 1), and has been found to be 0.5, clearly
indicating a bimolecular mode of termination.
Assuming the rate constants for all the propagation The intrinsic viscosity of the polymethacrylamide
steps to be the same, the rate of polymerization can be decreases on increasing the concentration of initiator
given as (fig. 2). Similar results have been given by Palit et al.
[16].
Rp = kp [M] [_/V/~] (7)
[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. 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.
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- Fig. 5. Arrhenius plot of initial rate of polymerization (Ri) vs recip-
tion (Rp) vs concentrations of methacrylamide. [KzS2Os] = 5.0 rocal of absolute temperature (T) of polymerization, [Methacryl-
10-4 tool. dm -3, [L-cystein hydrochloride] = 2.0 x 10_3 mol. dm -3 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 to 40 ~ and any further increase in temperature causes
The initial rate and maximum conversion increases a retarding effect on the rate as well as on maximum
with increasing monomer concentration (1.0 x 10-i _ conversion (table 4). At a higher temperature the rate
4.0 10 -1 mol dm -3 in table 3). The monomer expon- of termination by bimolecular interaction is faster than
ent has been found to be close to unity (fig. 4). The the propagation. The overall energy of activation has
deviation in the monomer exponent at a higher con- been calculated from the Arrhenius plot (fig. 5) and has
centration of monomer can be explained in terms of a been found to be 53 _+ 1 KJ/mole. From the results
cage effect i. e., at higher concentrations of monomer given in table 4, it is clear that the intrinsic viscosity
the free radicals are imprisoned in a solvent cage, decreases on increasing the temperature, thereby it
which reduces the total concentration of active radi- reveals that the degree of polymerization decreases at a
higher temperature.
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 Effect of additives
intrinsic viscosity increases linearly up to 2.0 x 10 -1 The effect of inorganic salts MnSO4 94H20; KCL
mol dm -3 concentration of monomer, thereafter the and Na2C204 have been studied. Figure 6 clearly
steady increase in intrinsic viscosity is not maintained. 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
Temperature effect medium. Similarly in the presence of sodium oxalate,
The rate of polymerization and maximum conver- the initial rate of polymerization as well as maximum
sion increases on increasing the temperature from 20 ~ yield decreases which is due to the production of oxa-
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
[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).
[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)
[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