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Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142

© Scholarlink Research Institute Journals, 2011 (ISSN: 2141-7016)

Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)

Amine Peroxide Initiated Polymerization Reactions:

Effect on Molecular Weight

M.K. Oduola and L. Uyigue

Department of Chemical Engineering,

University of Port Harcourt, PMB 5323, Port Harcourt, Nigeria
Corresponding Author: M.K Oduola
Limitations often encountered in the polymer molecular weight MW and molecular weight distribution MWD
has promoted research into unconvectional free radical initiators. A traditional free radical macromolecular
initiator has recently been investigated for peroxide modification of the surface of disperse fillers and pigments
with the objective to enabling their participation in the elementary reactions of polymerization: initiation, chain
propagation and termination, resulting in the formation of an interfacial polymer layer with macromolecules
grafted to the surface. Polymerization kinetics of vinyl monomers initiated by this amine-containing initiator
under homophase and heterophase conditions has been examined with respect to the effect on the resulting
polymer MW by means of dilatometric and viscosimetric measurements. Poly(methyl methacrylate) formed
under corresponding conditions is characterized by about 2-3 times higher values of MW as compared to
polystyrene. In particular, significant deceleration of the termination reactions upon interaction of growing
macroradicals due to diffusion complications has been observed. High polymerization rate with the production
of high-MW products resulting from the application of high-MW initiator, as compared to convectional low-MW
peroxides has been attributed to the polymerization – polyrecombination mechanism of the formation of
Keywords: Free-radical polymerization, surface-attached radicals, peroxide oligomer, molecular weight

Free-radical polymerization is a very versatile homopolymers with narrow molecular weight
polymerization reaction mechanism that is applicable distributions (MWD), and eventually block
to a wide range of vinyl monomers. The resulting copolymers. Many techniques have been developed
polymeric materials can be used in a variety of that are based on reversibly terminating the growing
applications from packaging materials to coatings as polymeric radicals, like nitroxide mediated
well as automotive parts. These different applications polymerization (NMP), atom transfer radical
require different material properties, which are polymerization (ATRP) (Wager et al., 2004; Lu et al.,
determined amongst others by the microstructure of 2010) and reversible addition fragmentation chain
the polymer chain, the interactions between the transfer (RAFT) (Yu et al., 2009; Nese et al., 2010).
chains and the types of additives. When we focus on Together, these form the field of controlled radical
the microstructure, we can distinguish polymers that polymerization.
differ in the structure of the backbone, in molecular
weight (MW), in composition and in end groups The challenge of producing polymers with peroxide
(Voronov et al., 2000). moieties arose in the 1960s thanks to the need for
chemical modification of convectional polymers. As
However, in free-radical polymerization it is compared to traditional low-molecular-weight
impossible to obtain a polymer in which all chains peroxides, these peroxide polymers have been found
have exactly the same structure. They will differ in to exercise a more significant influence on the MW
length, composition, end groups and backbone and MWD of the polymers being formed (Murthy
structure, even when all chains are initiated at exactly and Kishore, 1996). In addition, they can participate
the same moment and in the same way. During the in the formation of block, graft, brush-like
polymerization these structural differences will copolymers, interpenetrating polymer networks and
usually become larger as the ratios of the different so on (Bachmann et al., 2007).
components in the reaction mixture change. So it is
not easy to control the polymerization and thus to Application of unconventional free-radical
obtain polymers with a predefined structure. polymerization initiators has been encouraged in
In the past three decades several techniques have recent years owing to their capabilities to eliminate
been developed to control one or more aspects of the the limitations encountered with the use of traditional
chain structure. Many of these are aimed at producing ones. These include unmanageable rate of
Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)

polymerization (in particular, when block polymers both under homophase conditions in
are needed (Bartel et al., 2008), and limited MW of comparison with the surface attached
the resulting polymers (Minko et al., 1999; Voronov macroinitiator resulting from tethering of
et al., 2000). More often than not, polymerization rate macromolecular initiator to solid disperse
increases with increasing initiator concentration, but surface; and
at the same time, the molecular weight (MW) of the 2) to gain a better understanding of free-
resulting polymers is reduced. This undesirable effect radical polymerization mechanism involving
could be thwarted by employing unconventional this unconventional initiator, and to describe
initiators (Calvin et al., 2000; Kushanov, 1991; the observed MW dependences from a
Ivanchev et al., 1989; Murthy & Kishore, 1996). mechanistic point of view.
As an example, it has been shown that application of
acyl peroxide initiators leads not only to a rise in MW EXPERIMETAL
with increasing conversion, but also narrows the Materials
molecular weight distribution (MWD) of the resulting The organic solvents employed were purified prior to
polymers (Ivanchev et al., 1983). The presence in the use by employing the corresponding techniques
initiator structure of a second radical generating (Waysberger et al., 1958). The 2,2’-
functionality causes its entrance into the growing azobisisobutyronitrile (AIBN) was purified by
macrochains to form macromolecules, which recrystallization from ethanol and dried under
consequently become active participants of chain re- vacuum. As mineral substrates, Titanium Dioxide in
initiation, propagation, transfer and termination pigment form TiO2 is of rutil modification “RSL-2”
reactions (Calvin et al., 2000). These additional grade, surface area of 1.87 m2·g –1 and water рН of
functional groups present in the initiator molecules 7.0 was used without preliminary purification. All
however lead to sufficiently complex polymerization other reagents with analytical grade were purified by
kinetics, and as a consequence unpredictable MW standard procedures or used as received.
characteristics and MWD. This is aggravated by the
fact that polymer peroxides have been little Modification of pigment surface
investigated with regards to their initiating Modification of pigment surface was performed via
characteristics upon free radical polymerization of the adsorption of oligomers from their acetone
vinyl monomers as compared to conventional organic solution at room temperature. For this purpose in a
peroxides. rector equipped with a mechanical stirrer 1% acetone
solution of oligomer was initially prepared, after
Recent papers have been devoted to the systematic which the pigment was added under intensive
investigation of the initiating properties of a low- agitation (200-300 rpm) in a 1:4 wt ratio to solvent.
molecular-weight amine peroxide 2–[(-,-'-di-tert- The suspension was then maintained under agitation
butylperoxy methyl)amino] ethanol (DP2), an for 1 hour and separated by a centrifuge (8000 rpm).
oligomer initiator, amine peroxide macroinitiator Following multiple rinsing with acetone and
(APM), obtained as a result of polymer modification centrifugation the pigment was dried to constant
of maleic anhydride copolymer with methyl weight at room temperature and the drying process
methacrylate – poly[methyl acrylate-со-maleic was controlled by sample weight loss.
anhydride] by reaction with DP2, as well as in-situ Oligomer adsorption, as well as the amount of
formed macroinitiator on TiO2 pigment surface grafted polymer at the pigment surface were
(TiO2−mod−APM) for polymerization of two model estimated gravimetrically by the weight loss upon
vinyl monomers: styrene St and methyl methacrylate oven drying at 973 К. Amount of organic substances
MMA. (Oduola, 2009; Oduola et al., 2007). in the pigment under investigation (А, mg/g) was
Investigation on these two monomers, differentiated determined from the relation:
by polarity and chain termination mechanism, will А = [(m2 –m0)/(m1-m0)] × 1000 (1)
not only facilitate the elucidation of the problem where: m0 – weight of empty bucks, g; m1– weight
described above, but also go a long way to throw of bucks plus pigment prior to oven drying, g; and m2
more lights in the general mechanism of vinyl – weight of empty bucks plus pigment after oven
polymerization involving polyreactive drying, g.
macroinitiators, as well as highlight their advantage
over convectional initiators. Investigation of vinyl polymerization kinetics
Homophase and heterophase polymerization kinetics
In the light of the above-mentioned facts, the aim of was investigated dilatometically following the
this investigation is two-fold: procedures earlier reported (Oduola, 2009; Oduola et
1) to further examine the effect on the resulting al., 2007). Polymerization process was carried out
polymer MW of initiating the free-radical upon intensive agitation on a magnetic mixer in the
polymerization of Styrene (St) and Methyl temperature range 333…380 ± 0.1 К. Conversion was
Methacrylate (MMA) initiated by an estimated from the dilatometer data on monomer
unconventional amine-containing initiator volume reduction, and confirmed gravimetrically by

Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)

the amount of precipitated polymer at the end of the Table 1. Influence of various factors on the molecular
process. weight of the resulting polymers

Viscosity measurement v·10

Viscosities are of interest in polymer technology in [I]0·102, 4
, Mη· DP·
Monomer mol/ Initiator T, К S, %
order to follow the course of a polymerization mol/L mol/ 10-3 10-2
reaction or to monitor continuously the quality of a L
product. In most cases viscosity is measured by 2.90 DP2 3.00 353 30.7 1.39 24.2 2.3
capillary viscometers or rotating viscometers. For
0.65 33.3 2.06 71.4 6.9
polymer systems, solution or melt, the viscosity can 370
be related to the MW of the polymer (Rodriguez et 5.80 APM 1.31 36.4 2.17 60.8 5.8
al., 2003). MW was estimated from the intrinsic 1.96 39.4 2.93 48.3 4.7
viscosity values [η] determined by viscosimetry with St
TiO2−m 333 14.2 1.56 180 17.
the aid of Mark-Hawing equation relating [η] with 5.80 od−AP 2.00 353 13.0 2.20 142 3
the MW: M 6
370 23.4 3.21 82.5 7.9
[η] = К МW α (2)
where: К and α are constants for a given polymer 5.80 AIBN 1.00 370 48.5 4.90 38.9 3.7
solvent system at a particular temperature. 3.11 DP2 3.00 353 41.0 3.87 49.3 4.9
% of grafted polymer, G, at the pigment 6.23 3.00 – 4.22 105 10.
surface was determined gravimetrically from the 3.11 APM 353 17.3 1.65 69.4 4
difference between the organic content in the pigment 1.80
6.23 19.8 3.55 139 13.
prior to and after polymerization using equation 3 MMA
0.57 17.0 2.03 519 9
below: TiO2−m
G = [(А2 –А1)/(А1)] × 100 (%) (3) 6.23 od−AP 1.15 370 23.8 3.16 306 8
where: А1, А2 are the organic content at the pigment M 1.72 26.6 3.61 215 5
surface prior to and after polymerization respectively, 4
6.23 AIBN 1.80 353 51.9 10.1 68.7 6.9
Source: (Oduola, 2005)
The concept of MW enhancement with the aid of It has earlier been established that the pigment
non-convectional radical initiators described above surface participates not only in chain transfer
was further buttressed by the data obtained on reactions, but also affects all other elementary stages
investigating the effect of various factors on the MW of polymerization (Oduola et al., 2007). Indeed, the
of polymers formed during the polymerization of St kt/kp2 ratio upon transition from vinyl polymerization
and MMA (Table 1). in dioxane to the polymerization initiated by TiO2–
mod–APM is decreased by a factor of 2-3. This could
It should be emphasized that in all cases, poly(methyl be explained by a significant deceleration of the
methacrylate) PMMA formed under corresponding termination reactions upon interaction of growing
conditions is characterized by about 2-3 times higher macroradicals due to diffusion complications. For
values of DP as compared to polystyrene (PSt), PMMA, the MW is also less temperature dependent,
which is easily explainable by the essential which could be correlated with a lower reduction of
differences in the ratio of propagation rate constant the initiator efficiency with increasing temperature as
(kp ) to termination rate constant (kt ) for these contrast to styrene, as well as termination due to
monomers (Rodriguez et al., 2003). For both proportionation, as against recombination for the
monomers the degree of polymerization DP latter. Of remarkable interest was the study of the
symbiotically rose upon transition from initiation by effect of the yield of styrene on the resulting polymer
low-molecular-weight DP2 via its oligomer DP value during APM-initiated polymerization (Fig.
derivative APM to TiO2−mod−APM. Moreover, 1). It is apparent from the plot in Fig. 1 that the
comparison of initiation by aminoperoxide with polymer MW rises continuously as polymerization
AIBN has shown that in the former case, polymers proceeds. This is a remarkable difference as
with lower MW are formed even at low rates of compared with the polymerization process initiated
polymerization due to the occurrence of chain by the low-molecular weight initiator DP2, for which
transfer reactions to the initiator. the polystyrene MW does not increase with
conversion. The observable fact of polystyrene DP
enhancement during polymerization initiated by
oligoperoxides could be explained by the introduction
of polymerization – polyrecombination mechanism of
the formation of macromolecule.

Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)




10 20 30 40
Конверсия, % %
Figure 1. The kinetic relationship of the degree of polymerization DP with monomer conversion during
initiation by an amine peroxide macroinitiator at 353К: in dioxane–1,4 ([M]0 = 5.8 mol/L, [I]0 = 0.02 mol/L).

This can be illustrated as an example of the free-radical polymerization process, initiated by a polyperoxide,
whose reaction scheme could be presented in the following form:
(kd)→ R*(O–O)x (initiation)
R*(O–O)x + M (ki)→ R (O–O)x M*
R (O–O)x M* + (n – 1) M (kр)→ R (O–O)x Mn* (propagation)
R (O–O)x Mn* + R (O–O)x Mn* (kt)→ R (O–O)x Mn+1R (O–O)x (termination)
R (O–O)x Mn+1R (O–O)x (k´d)→ R (O–O)x Mn+1R*(O–O)y + R*(O–O)x-y
R (O–O)x Mn+1R*(O–O)y + M (k´i)→ R (O–O)x Mn+1R(O–O)yM*
Figure 2. Polymerization polyrecombination mechanism of formation of macromolecules during oligoperoxide
initiated polymerization processes
R*(O-O)x,y – radical, containing peroxide (–О:О–) moieties, kd, ki, kp, and kt – rate constants for decomposition,
initiation, propagation and termination reactions respectively
As can be inferred from Fig. 2, the macromolecules
formed at the outset (as a result of the first series of high-molecular-weight products with the aid of high-
initiation, propagation and termination reactions) molecular-weight initiator, as compared to
during the polymerization of vinyl monomers contain convectional low-molecular-weight peroxides.
at their ends peroxide moieties as segments of the Throughout the period of solution polymerization
original initiator. process initiated by a surface-attached macroinitiator,
polymer formation is observed both on the surface
These active macromolecules are subsequently and in the solution. This is due to the initiation of the
involved in the polymerization process through their polymerization in solution by, in particular, desorbed
manifold decomposition (at the stages of re- macroinitiator from the surface at the increased
initiation), thereby leading to increasing polymer process temperature, and other active radicals formed
MW with increasing monomer conversion. The re- during the decomposition of the surface-attached
initiation frequency is determined by the number of macroinitiator. The time dependence of MW of the
peroxide moieties incorporated into the non-grafted polymer formed in solution alongside
macromolecule and it is dependent on the with the amount of polymer grafted onto the solid
functionality of the macroinitiator employed for the surface for a polymerization process initiated by the
polymerization process. For the same reason, it is surface attached macroinitiator TiO2−mod−APM
possible to combine high polymerization rate with the have been examined (Fig. 3).
production of

Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)

mg/g g

time, hrs
Figure 3. Kinetics of the change in the grafted PMMA onto TiO2 surface (G, mg/g), yield (Y, g) and degree of
polymerization (DP) of non-grafted PMMA upon polymerization, initiated by TiO2−mod−APO in dioxane−1,4
at 338 K (Oduola, 2005).

The character of the process occurring in solution has grafted homopolymer the polymer conversion has
been found to be highly distinctive from the grafting been observed to rise continuously throughout the
process onto the pigment surface. Whereas polymer duration of the process, what may be the outcome of
formation in the bulk occurs with a steady rate the above-described degradation-polymerization
throughout the period of the investigation (plot of mechanism involved in the creation of such polymer
yield vs time Y on Fig. 3), the amount of graft poly parts.
(methyl methacrylate) increases linearly only within
the first 2½ hours, then it is retarded with increasing COCLUSIOS
conversion and a “plato” value is attained after nearly Polymerization kinetics of Styrene and Methyl
3½ hours, as can be seen from the plot of G vs time Methacrylate initiated by an unconventional amine-
in Fig. 3. Attainment of the plato value upon graft containing initiator under homophase and
polymerization from the surface is well known and heterophase conditions has been examined with
has been observed by a number of researchers respect to the effect on the resulting polymer MW.
[Velten et al., 1999a,b; Minko et al., 1999]. The Poly(methyl methacrylate) formed under
termination of the growth of grafted polymer at the corresponding conditions is characterized by about 2-
solid surface takes place at a certain graft density, i.e. 3 times higher values of DP as compared to
at a definite value of grafted macromolecules per unit polystyrene. It is evident that the involvement of
surface area. At this moment the macromolecular TiO2 particles with the surface-attached radicals in
chains are so densely packed (laterally condensed), the heterogeneous polymerization process profoundly
that the formation of new polymer chain definitely influenced all the elementary stages, particularly
leads to scission of the previously formed grafted chain transfer and termination. In particular,
macromolecules as a result of the dissociation of the significant deceleration of the termination reactions
С–С bond in the main chain. On the contrary, despite upon interaction of growing macroradicals due to
being hindered by increasing diffusion barrier by the diffusion complications has been observed. The
graft polymer layer, the formation of low-molecular observable fact of polystyrene DP enhancement
weight radicals on the surface is not completely during polymerization initiated by oligoperoxides
brought to a halt and, as a consequence, the could be explained by the introduction of
polymerization process is not terminated in solution. polymerization-polyrecombination mechanism of the
formation of macromolecule. It is therefore possible
There is also the possibility of degradation- to combine high polymerization rate with the
polymerization mechanism of polymer build up in the production of high-molecular-weight products with
bulk. This means that at a definite graft density the the aid of high-molecular-weight initiator, as
creation of new chains at the surface is only feasible compared to convectional low-molecular-weight
upon degradation of the existing chains, which are peroxides.
displaced from the graft layer and are relocated from
the surface to the solution. Furthermore, for the non-
Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)

ACKOWLEDGMETS Nese, A.; Yungwan Kwak; Renaud Nicolaÿ; Michael

It is a great pleasure for us to thank Prof. Viktor Barrett; Sergei S. Sheiko; Krzysztof Matyjaszewski,
Tokarev and Prof. Stanislav Voronov of the National 2010. Synthesis of Poly(vinyl acetate) Molecular
University “Lvivska Polytechnika” in Ukraine for a Brushes by a Combination of Atom Transfer Radical
lot of help and for numerous discussions throughout Polymerization (ATRP) and Reversible Additional
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Journal of Emerging Trends in Engineering and Applied Sciences (JETEAS) 2 (1): 137-142 (ISSN: 2141-7016)