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Hunkeler - 1991 - Mechanism and Kinetics of The Persulfate-Initiated
Hunkeler - 1991 - Mechanism and Kinetics of The Persulfate-Initiated
D. Hunkeler
Received April 12, 1990; Revised Manuscript Received August 29, 1990
complex” mechanism, in which hydrogen bonding between the monomer and initiator lead to association,
has been derived. This postulates that the monomer-initiator associate leads to donor-acceptor interactions
between the amide and the persulfate. The decomposition of this charge-transfer complex leads to a secondary
initiation reaction, which proceeds in competition with and often in preference to the thermal bond rupture
of the peroxide. It will be shown to give good quantitative prediction of the polymerization rate order,
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monomer and initiator consumption, and molecular weight. Furthermore, the mechanism avoids the free-
energy inconsistencies characteristic of prior theories and is generalizable to other nonionic and ionogenic
acrylic water-soluble monomers in polar solvents.
Rp
=
fc[M]L25[I]0'5 (1) K'
1. I+ ^ I-M
Over the past two decades, 22 investigations have con-
firmed a monomer dependency exceeding first order while
maintaining that termination occurs predominantly 2. I-M R/ + Rin*
through a bimolecular macroradical reaction.10 Riggs and
Rodriguez11 interpreted the high rate order as evidence of Matheson’s alternative explanation for the initiation mech-
monomeric influences on the rate of initiation. This had anism assumes that as two fragments of a dissociated
previously been postulated by Jenkins12 to account for molecule are produced they are contained in a “cage” of
similar observations made while polymerizing styrene in solvent molecules. This radical pair may combine several
toluene with benzoyl peroxide as an initiator. Morgan13 times before diffusing out of the cage. This hypothesis is
had taken the inference a step further, suggesting his ses- based on Eyring’s (1940) observation24 for benzene at room
quimolecular order was attributable to secondary initiation temperature, where a molecule made 1010 movements in
caused by the monomer-enhanced decomposition of per- its equilibrium position per second but underwent 1013"14
oxide. The credibility of this hypothesis has been en- collisions in the same period. For the persulfate-initiated
hanced through experimental work performed by Dainton polymerization of acrylamide the cage-effect theory can
and co-workers.14"17 They observed the rate dependence be written as
by a decrease in the overall activation energy. This was (2) The electrical environment of the monomer is the
observed by the same authors several years later for primary factor in its interaction with peroxide.
reactions between benzoyl peroxide and aminated poly- (3) Monomer-enhanced decomposition is limited to
styrene,32 indicating that the donor-acceptor interactions initiator molecules where the radical pair has achieved a
are not dependent on molecular architecture. minimum “critical” separation.
In 1978, Trubitsyna33 used conductivity to monitor the (4) The enhanced decomposition of complexed persul-
charged particles produced from the interaction of acry- fate is caused by hindered recombination and not a greater
lamide and potassium persulfate. These experiments frequency of fragment dissociations. When the initiator
found the onset of charged particle generation corre- is bound to the monomer, the dissociated radical pair
sponded to the induction period of the reaction and the cannot regenerate potassium persulfate by recombination.
onset of radical generation, as determined by ESR. Either radicals or an inert recombination product of the
Furthermore, they were performed below 20 °C, where form O^SOsMOaSO*- are produced. Therefore, in the
the thermal decomposition of potassium persulfate is presence of donor-acceptor interactions, each radical
negligible, indicating a secondary decomposition reaction separation or “transient dissociation” results in the con-
was occurring. On the basis of these observations, Tru-
sumption of one initiator molecule. In the absence of
bitsyna33 proposed an electron donor mechanism, with bound monomer, an initiator transiently decomposes and
concurrent radical and charge generation. recombines 102"3 times for each “permanent decomposi-
Morsi34 observed that diphenylamine enhanced the tion”.
decomposition of benzoyl peroxide. He also attributed
this to a donor-acceptor interaction between the amine Elucidation of an Initiation Mechanism
and the peroxide and suggested the interaction was caused
by a modification of the peroxide’s dihedral angle. Further Complex-Cage Equivalence. We have shown in the
evidence that acrylamide associates with potassium per- preceding section that the formation of an intermediate
sulfate comes from Bekturov,38 who found SO42" salted “associate” is a necessary precursor to monomer-enhanced
out poly(vinylpyrrolidone) but could not precipitate poly- decomposition. This allows the electron-donating group
acrylamide, presumably because it was neutralized by a
sufficient time to attack the peroxide to be competitive
reaction with the amide side chains. The reaction of with the rapid radical fragmentation and recombination
amides with persulfate is not surprising in light of NMR reactions. This monomer-initiator associate can result
evidence36 that shows that the carbonyl groups are from either the diffusive displacement of a monomer to
the volume element of the peroxide (cage approach) or
hydrogen bonded to water but the amides are relatively
free. Coleman37 has confirmed that the carbonyl and the formation of a molecular complex. Both of these
amide substituents behave complementarity in that the phenomena can be represented by a general reaction that
is nonspecific to the forces drawing the monomer and
binding of one functional group is concurrent with the
reactivity of the second. initiator into close proximity. (This modification must
also be applied to Manickam’s mechanism to successfully
Chápiro38 conducted an extensive investigation of the
solvent effects on acrylamide polymerization and reported: apply it.)
^ ^ ^p,methanol ^ ^p,DMF IRin’ ’Rint + M JjV)
—
^p,water ^p,acetic acid
~
Proposed Mechanism. The apparent increase in the (S04*~ ~*04S), and “diffuse cage fragments” ISO*·" -O4S).
association constant (k,) with temperature can be ratio- The total persulfate in the system (Jt) is
nalized if we consider association, and the donor-acceptor
reactions, to. proceed within the framework of a caged h [S2082"] + (S04—*04S) + |S04—*04S)
=
(6)
mechanism. Reactions of the sulfate radical that generate where
nonreactive products must also be included to account for
low efficiencies of initiation (f = 0.06-0.4).
Initiator Reactions (Formation of a Caged Hier- =
[S2082"]
archy).
=
(S04—O4S) xIt
1. S2082-^(S04—*04S)
(S04-O4S| =
/,
2. (S04- -04S) - (S04- -04S|
and + + 2 = 1.0.
*
3. (S04--O4S) 2S04- The balances on all reactive species follow:
4. {SO/"O4S}-S2082- d[Sd°8
=
-*i[S2082"] + *V(S04—O4S) +
4dt AxISgOg2-]
composition.
5. association
d|S0/""O4SI =
fed*|S04--04S}
-
A2(S04—O4S)
-
-.........4dt.....-4-j
|so4‘-o4si + m-(so4-m*o4s| *r{S04--04S¡-k*\SOp-04S|[M] (9)
6. dissociation through a donor-acceptor intermediate dfso4‘- -04sj
|s°rM‘°4S)
-
S04- + HS04- + CH2C*C(0)NH2 J-5P-1 =
fea*|S04-O4S}[M]
-
+ (10)
7. -L Q (inert products) (fcb Ac)|so4- m-o4s|.o
Step 7 represents the consumption of monomer-initiator
associates through a reaction that generates nonreactive
products. This initiator deactivation is necessary to avoid
^P -
^•ISO.-O.SI + kjsor M-o.s|.
~ 0 (11)
feH[S04-][H20] Aa[S04*-][M]
-
From eq 10
9. S04- + H20 ^ HS04" + ‘OH
-
(W
10. + M -»
Rj*
Is0-'" m'°-s} (^)IS0-“"0-s»Mi
Assuming kp is independent of chain length (ku k& = -
decomposition are not observed and the rate order reverts These decompose to produce two macroradicals of length
to unity.47·48 Ergozhin49 investigated the kinetics of a series 1 (when 1:1 complexes are produced, one primary radical
of N-substituted amides and observed the rate order with is liberated). Such a mechanism reduces to a second-order
respect to monomer concentration to decrease as the rate dependence on monomer concentration, in agreement
accessibility to the vinyl group was hindered. This with experimental observations for diallyldimethylam-
confirms Trubitsyna’s postulate33 that the amide is monium chloride polymerization (Jaeger, 1984).55 Jaeger
responsible for the electron rearrangement leading to the also showed that the rate order was reduced by 1 when a
monomer-initiator association. Haas50 has observed that noncomplexing initiator [azobis(pentanoic acid)] was used
other amide-containing monomers, for example, acrylyl- in place of potassium persulfate. Therefore, the high rate
glycinamide, enhance the decomposition of potassium per- orders observed for polymerization of acrylic water-soluble
sulfate and have the same rate order with respect to monomers in aqueous media initiated by persulfate are
monomer concentration as acrylamide, which is again almost certainly due to hydrogen-bonding and ionic
consistent with a hydrogen-bonded associate. If meth- interactions between the monomer-initiator pair. The
acrylamide replaces acrylamide as the monomer in a per- strength in this interaction determines the deviation in
sulfate reaction, a greater than first-order dependence is order from unity. Table II summarizes the observed
again observed (Rp = A/1·13; Gupta, 1987).51 The reduced kinetic relationships for several nonionic, anionic, and cat-
order from the s/4th power may be an experimental ionic acrylic water-soluble monomers. A correlation
anomaly, as methacrylamide has not been extensively between the rate order with respect to monomer and the
investigated. However, it is more likely that the a-methyl strength of the monomer-initiator complex is again
substitution is affecting the electron arrangement neces- observable.
sary to produce a monomer-initiator complex.52 (Meth- On the basis of the preceding literature survey, we can
acrylamide radicals are present in a resonance-stabilized propose the following general initiation mechanism for
structure where the /3-carbon can more easily stabilize a acrylic water-soluble monomers with persulfate:
radical than the -methyl-substituted carbon.53)
1. S2082"^(S04—O4S)
Table II summarizes the observed kinetic relationships
for several acrylic water-soluble monomers (acrylamide, 2. (S04—*04S)
—
{SO/"*04S|
acrylylglycinamide, acrylic acid, iV/V-dimethylacrylamide,
methacrylamide). There is a direct correspondence be- 3. |S04—O4S|-S2082-
tween the monomer’s hydrogen-bonding affinity and the
4. {SO/--'O4S| —
2S04~
rate order with respect to monomer concentration. During
the derivation of the hybrid cage-complex initiation mech- 5. SO/" + H20 —
HS04" +
anism, it was shown that high rate orders occurred
concomitant with monomer-initiator association. If we 6. SO/" + M —
R/
combine these two observations, then the hybrid mech-
anism infers that hydrogen bonding between the monomer 7. + M —
R/
and persulfate is the cause of association phenomena. This
seems intuitively reasonable and is quite probable. 8. (S04- -04S) + *M -
|S°4*' xM'°4S]
The sum of a first- and sesquimolecular-order initiation
mechanism, the hybrid cage-complex model, is therefore 9- + xRi'
|S°4*"xMO4Sh(2"x)Rm*
flexible enough to quantitatively describe a broad array
of kinetic observations for nonionic and anionic acrylic
^ O4SJ Q (inert products)
10. -
Table IV
Limiting Conversion versusMonomer and Initiator Figure 1. Conversion-time data ( ) for an acrylamide polym-
Concentration erization. The experimental conditions were [monomer] = 5.37
mol/Lw, [KzSíOg] = 2.44 X 10~3 mol/L,, and temperature = 50
limiting potassium °C. A limiting conversion of 0.97 is observed. Increasing the
conversion acrylamide persulfate concn, temperature to 60 °C (arrow) did not lead to consumption of
(Xi) concn, mol/L mmol/L additional monomer.
0.92 6.41 0.238
0.95 6.04 0.250
0.96 5.37 0.248
0.996 4.69 0.251
0.996 4.03 0.228
0.997 3.35 0.252
0.76 6.70 0.0609
0.999 6.70 1.573
Table V
Parameter Estimates
param value units
h 40 °C: 1.0 dimensionless
50 °C: 0.372
60 °C: 0.065
( 2*,*)0 40 °C: 3.17 X 10"6 L/mol-min TIME (minutes)
50 °C: 1.06 X10"3
60 °C: 1.93 X 10"2
k(E 2.433 X 10"9 dm2/mol-min
Aob 8.01 dimensionless
Aib 2.0 X 10'2 k->
(Kim and Hamielec, 1984)
0
kt =
(2) = 8.77 x 1041 exp(-66500/fiT). 6 A is a gel effect
parameter in the expression fctd°/ktd =
exp(Awp) where A =
Aq-
A,r.
concentration for aqueous polymerizations of cationic
monomers with persulfate.
Figure 3. (a) Conversion-time data ( ) and kinetic model Figure 4. (a) Conversion-time data ( ) and kinetic model
predictions (—) for an acrylamide polymerization at 50 °C: predictions (—) for an acrylamide polymerization at 50 °C:
[monomer] = 4.03 mol/Lw and [KgSgOg] = 0.228 X 10“3 mol/Lw. [monomer] = 4.69 mol/L» and [KgSgOg] = 0.251 X 10"3 mol/L,.
(b) Weight-average molecular weight-conversion data ( ) and (b) Weight-average molecular weight-conversion data ( ) and
kinetic model predictions (—) for the same experiment. kinetic model predictions (—) for the same experiment.
peak separation was optimized by varying the acetonitrile/ water each isolated monomer droplet contains all reactive species and
ratio. behaves like a microbatch solution polymerization reactor.
Molecular weights were measured by using a Chromatix Inverse-microsuspension polymerizations were performed by
KMX-6 low-angle laser light scattering photometer, with a cell using Isopar-K (Esso Chemicals) as the continuous phase and
length of 15 mm and a field stop of 0.2. This corresponded to sorbitan monostearate (Alkaril Chemicals) as the emulsifier. The
an average scattering angle of 4.8°. A0.45-gm cellulose/acetate/ aqueous phase consisted of recrystallized acrylamide monomer,
nitrate filter (Millipore) was used for polymer solutions. A 0.22- distilled deionized water, and recrystallized potassium persul-
µ filter of the same type was used to clarify the solvent. Distilled fate. The ratio of aqueous to organic phases was 0.74:1.
deionized water with 0.02 M NagSO< (BDH, analytical grade) Polymerizations were performed in a 1-gal stainless steel reactor,
was used as a solvent. Weight-average molecular weights were continuously agitated at 323 ± 1 rpm. This provided large particle
regressed from measurements of the Rayleigh factor using the diameters («10 µ ), which minimized interfacial effects. The
one-point method.62 This has been observed to reduce the error reactor was purged with nitrogen (Canadian Liquid Air, UHP
in light scattering 2-fold over the conventional dilution procedure. grade, 99.999% purity) throughout the polymerization. A
The refractive index increment of the solvent was determined complete description of the experimental procedures is given in
a prior publication.61
by using a Chromatix KMX-16 laser differential refractometer
at 25 °C and a wavelength of 632.8 nm. The dn/dc was found Experimental Conditions. Polymerizations were performed
to be 0.1869. isothermally at 40, 50, and 60 °C at monomer concentrations
between 25 and 50 wt % of the aqueous phase. The latter cor-
For polymerizations solid acrylamide monomer (Cyanamid responding to the solubility limit of acrylamide in water. Table
B.V., The Netherlands) was recrystallized from chloroform (Cale- III summarizes the experimental conditions for all polymeriza-
don, reagent grade) and washed with benzene (BDH, reagent tions. For all experiments reactor control was excellent, with
grade). Potassium persulfate (Fisher Certified, assay 99.5%) thermal deviations never exceeding 1 °C.
was recrystallized from double-distilled deionized water. Both
reagents were dried in vacuo to constant weight and stored over Results and Discussion
silica gel in desiccators.
Method of Polymerization. Polymerization at high monomer Rate Order with Respect to Monomer Concen-
concentrations in solutions requires chain-transfer additives to tration. The measured residual monomer concentrations
lower molecular weight, reduce viscosity, and provide more were used to calculate the initial rates of polymerization.
efficient heat transfer. However, for this experimental set, chain- A series of six experiments were performed at 50 °C with
transfer agents are undesirable since they can affect the initiation monomer concentrations between 25 and 50 wt % of the
mechanism through redox coupling with persulfate. Therefore, aqueous phase, varied in 5% increments. From these data
a heterophase water-in-oil polymerization process (inverse mi- the following rate equation was estimated:
crosuspension)63 was employed. This permitted high aqueous
phase monomer concentrations while maintaining a stable, in- Rp
<* AT1·34*012
viscid reaction mixture, ideal for the generation of reliable kinetic
data. A prior investigation had demonstrated that inverse-mi- The 95% confidence limits were determined from a non-
crosuspension and solution polymerization are kinetically equiv- linear least-squares estimation routine based on Mar-
alent if a water-soluble initiator is employed.10 In such instances, quardt’s algorithm. The 95% confidence interval sur-
2168 Hunkeler Macromolecules, Vol. 24, No. 9, 1991
1.0
n 0.8 -
'o
Figure 7. (a) Conversion-time data ( ) and kinetic model Figure 8. (a) Conversion-time data ( ) and kinetic model
predictions (—) for an acrylamide polymerization at 50 °C: predictions (—) for an acrylamide polymerization at 60 °C:
[monomer] = 6.41 mol/L, and [ ^ ß] = 0.238 X 10~3
mol/Lw.
(b) Weight-average molecular weight-conversion data ( ) and
[monomer] = 6.70 mol/L, and [KzSaOg] = 0.0609 X10'3 mol/L,.
(b) Weight-average molecular weight-conversion data ( ) and
kinetic model predictions (—) for the same experiment. kinetic model predictions (—) for the same experiment.
emulsifier was found to be -141 J/mol, typical of a Comparison of Kinetic Model to Experimental
termination reaction. It was not, however, significantly Data. Figures 2-9 show conversion-time and weight-
smaller than zero at the 95 % confidence level, and we can average molecular weight-conversion data and model
conclude that unimolecular termination with interfacial predictions for all experiments. The hybrid mechanism
emulsifier is thermally invariant over the range investi- is capable of predicting the initial polymerization rate and
gated. weight-average molecular weight well over a range of tem-
The complex-cage efficiency (fc) is observed to decrease peratures, monomer concentrations, and rates of initiation.
with temperature, implying the monomer-swollen cage The molecular weight behavior with conversion is typical
preferentially forms inert species rather than active of acrylamide polymerizations where transfer to monomer
radicals. This is consistent with limiting conversion data, dominates. A slight decrease in molecular weight with
which indicate that initiator deactivation is more favorable conversion (although statistically significant at the 90%
at higher temperatures. confidence level), and the increase with the initial monomer
The apparent association parameter (fea = $>2fca*) is found concentration, is evidence that a fraction of the chains are
to increase with temperature according to an Arrhenius terminated through a bimolecular process. The limiting
dependence. This has been reported previously for acry- conversion is also predicted well at low initiator levels and
lamide polymerizations initiated by potassium persulfate.9 moderate monomer concentrations but, however, is slightly
As was discussed in the derivation of the mechanism, this overpredicted when it occurs at very high conversions
is the manifestation of two independent phenomena: a (>90%). This is due to the authors’ personal preference
decrease in the specific association constant (fca*), which to obtain accurate kinetic parameters at the expense of
is entropically less favorable at elevated temperatures, fitting limiting conversion data. Consequently, initial rate
and an increase in the fraction of potassium persulfate data were given a greater weighting in the analysis to
present as diffuse cages ( 2). The latter, which is the only compensate for the larger number of residual monomer
form of potassium persulfate capable of participating in measurements at high conversions.
monomer-enhanced decomposition reactions, are more Figure 10 illustrates the relative magnitudes of thermal
abundant at high temperatures due to a greater frequency and monomer-enhanced decomposition of potassium per-
of radical diffusive displacements and a lower rate of radical sulfate. At the onset of polymerization the majority of
fragment recombination. The ability of the hybrid mech- chains are initiated through a donor-acceptor interaction
anism to quantitatively predict association phenomena, between the acrylamide and persulfate. This effect is most
without the thermodynamic inconsistency of the specific extreme at elevated temperatures. As the conversion rises,
association parameter increasing with temperature, is a both the monomer and initiator have depleted (Figure 11)
second major advantage over the unmodified cage-effect and thermal bond rupture of the peroxide becomes the
and complex theories. predominant initiation reaction. Figure 11 also shows that
All other rate parameters (kp, kt¿, kim, k&) were obtained the rate of consumption of initiator is strongly dependent
from the literature and have been summarized in a prior on the initial monomer concentration. Furthermore, for
publication.63 the conditions of the simulation, the potassium persulfate
2170 Hunkeler Macromolecules, Vol. 24, No. 9, 1991
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