Monomer-containing manganese complexes in polymerization of methyl methacrylate and styrene

Article abstract of DOI:10.1134/S1070427211100235

Polymerization of methyl methacrylate and styrene in the presence of manganese cyclopentadienyl carbonyl-olefin complexes, with styrene and methyl methacrylate as olefins, was studied. The molecular-weight distribution of the polymers obtained was examined.

Full text of DOI:10.1134/S1070427211100235

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 10, pp. 1813−1820. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.V. Pavlovskaya, E.V. Kolyakina, E.S. Kotlova, L.N. Gruzdeva, D.F. Grishin, 2011, published in Zhurnal Prikladnoi Khimii, 2011,
Vol. 84, No. 10, pp. 1721−1728.
MACROMOLECULAR COMPOUNDS
AND POLYMERIC MATERIALS
Monomer-Containing Manganese Complexes
in Polymerization of Methyl Methacrylate and Styrene
M. V. Pavlovskaya, E. V. Kolyakina, E. S. Kotlova,
L. N. Gruzdeva, and D. F. Grishin
Research Institute of Chemistry, Lobachevsky Nizhni Novgorod State University, Nizhni Novgorod, Russia
Received March 1, 2011
Abstract—Polymerization of methyl methacrylate and styrene in the presence of manganese cyclopentadienyl
carbonyl–olefin complexes, with styrene and methyl methacrylate as olefins, was studied. The molecular-weight
distribution of the polymers obtained was examined.
DOI: 10.1134/S1070427211100235
Variable-valence metal complexes are widely used
in preparation of polymeric materials with preset
properties and characteristics [1–5]. Catalytic systems
based on transition metals ensured essential progress
in polymer technologies [6, 7]. Further progress
in improvement of polymer synthesis processes is
associated with the use of catalysts of a new generation,
“metallocene” catalysts [8, 9]. Today metal complex
catalysts are widely used for metathesis polymerization
of olefins [10, 11], polymer synthesis by the “living”
chain mechanism [1, 2, 5], and other polymerization
processes. Examples of metal complex catalysts
are stable transition metal complexes containing
η2-coordinated monomeric units [12]. Data on their
possible use for initiating the polymerization of vinyl
monomers are limited to a single paper [13].
In the context of studying the catalytic activity of such
metal complexes and developing new initiating systems
for the polymerization of vinyl monomers, it seemed ap-
propriate to study the specific features of the polymeriza-
tion of methyl methacrylate (MMA) and styrene (ST) as
the most commercially significant monomers in the pres-
ence of stable manganese cyclopentadienyl (Cp) carbonyl
complexes containing a coordinated monomer molecule
[scheme (1)], and also of formulations based on these
complexes and various halogenated organic compounds
(carbon tetrachloride ССl4, ethyl 2-bromoisobutyrate
EIB-Br, isoamyl iodide i-C5H11I) (Scheme 1).
Undoubtedly, the use of such compounds in polymer-
ization processes will allow the most detailed evaluation
of the effect exerted on the macromolecule synthesis not
only by the metal coordination sphere, but also by its
Scheme 1.
H
C
CH3
Ph
COOCH3
C
Mn
Mn
C
C
OC
OC
H
H
H
OC
5-Cyclopentadienyl-
dicarbonylmanganese
OC
5-Cyclopentadienyl-
methacrylate)dicarbonylmanganese
H
η
η
2-(methyl
η
η
2-styrene-
1813

1814
PAVLOVSKAYA et al.
ligand surrounding.
where mpol and mmon are the weights of the polymer and
monomer (g), respectively.
EXPERIMENTAL
The molecular weight and molecular-weight dis-
tribution (MWD) of the polymers were determined
by gel permeation chromatography on an installation
(Knauer) with a linear column (separation limit 2 × 106
Da, Phenomenex, Nucleogel GPCM-10, USA) or with
a cascade of two columns (Phenomenex Phenogel, pore
size 103–105 Å). As detectors we used a K-2301 differ-
ential refractometer and a K-2501 UV detector. For the
calibration we used close-cut references based on poly-
styrene (PST) and poly(methyl methacrylate) (PMMA).
Chromatographic data were interpreted using ChomGate
software.
The metal complexes were prepared by the general
procedure of the synthesis of manganese olefin complexes
Сp(CO)2Mn(η2-alkene) [14]. Cymantrene and the cor-
responding monomers (ST or MMA) were irradiated in
hexane in an argon stream with a 125-W mercury UV
lamp at –10°С for 45 min. According to IR data, within
this time the conversion of the starting cymantrene was
complete. The resulting solution was filtered, concen-
trated in a vacuum to a volume of 30 ml, and cooled
in a Dewar flask with dry ice for 12 h. The crystalline
precipitate formed in the process was filtered off and
recrystallized from hexane.
The 1Н NMR spectra of the polymers were recorded
with a Bruker DPX 200 spectrometer (solutions in
CDCl3).
Hexane, chloroform, toluene, and other organic sol-
vents were purified by common procedures. The physi-
cochemical constants of the solvents corresponded to
the published data [15]. The monomers were washed to
remove the inhibitor with a 10% aqueous alkali solution
and then with distilled water to neutral reaction, dried
over calcium chloride, and purified by distillation under
reduced pressure. Fractions with the following boiling
points were collected: MMA, 38°С/15 mm Hg; ST,
48°С/20 mm Hg [16]. When CCl4, EIB-Br, or i-C5H11I
was used as coinitiator, it was taken as a freshly prepared
0.1 M solution in toluene.
In the series of the known transition metal complexes,
manganese-based systems are relatively cheap and com-
mercially available. For example, Bamford and Finch
[17] found that cyclopentadienyltricarbonylmanganese
(CTM) and methylCTM in mixtures with CCl4 can initiate
the MMA polymerization. They showed that, in thermal
polymerization, CTM acts as inhibitor. Because the ligand
surrounding often plays a key role in the activity of a met-
al complex in the initiation of polymerization processes
[1, 2, 5], it is logical to assume that the coordination of
monomer molecules to the metal atom can significantly
affect the reactivity of manganese complexes, creating
favorable conditions for the polymerization initiation.
Therefore, we examined the initiating power of a series
of manganese complexes (CTM and its analogs contain-
ing monomeric ligands) in the polymerization of ST and
MMA as the most commercially significant monomers
in a wide temperature range, 25–100°С, both in the pres-
ence of halogenated organic compounds (ССl4, EIB-Br,
i-C5H11I) and without them. These halogenated organic
compounds, on the one hand, are frequently used as
coinitiators in radical polymerization in the presence of
metal complexes [1, 2, 5] and, on the other hand, can act
as chain-transfer agents in radical polymerization [18].
The samples were prepared as follows: Accurately
weighed portions of the monomer, initiator, and man-
ganese complex were placed in glass ampules. The
ampules were deoxygenated by freezing the mixture in
liquid nitrogen and pumping to a residual pressure of less
than 1.3 Pa, after which the polymerization at a definite
temperature was performed.
The polymerization kinetics was monitored gravi-
metrically under isothermal conditions. The ampule was
placed in a thermostat for a definite time. Then the ampule
was withdrawn and frozen in liquid nitrogen to stop the
polymerization. The resulting polymers were precipitated
into hexane. To remove the unchanged monomer, initiator,
and metal complex from the polymer, the samples were
reprecipitated two times and vacuum-dried to constant
weight, after which the conversion (%) was calculated
by the formula
It was demonstrated by the examples of CpMn(CO)2СТ
and CpMn(CO)2MMA that the binary initiating systems
based on these compounds in combination with ССl4 are
very effective in the polymerization of vinyl monomers.
For example, the MMA polymerization is initiated
with the above manganese complexes already at 25°С
(Table 1).An increase in temperature leads to an increase
P = mpol/mmon × 100,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

MONOMER-CONTAINING MANGANESE COMPLEXES
1815
Table 1. Molecular-weight characteristics of PMMA synthesized in the presence of CTM and manganese η2-olefin complexes
(0.125 mol %) at various temperatures
Coinitiator (0.25
Manganese complex
CTM
T, °C
80
τ, h
21
Conversion, %
Mn × 10–3
860
110
165
236
433
–
Mw/Mn
4.2
9.2
9.8
2.6
2.8
–
mol %)
ССl4
95
16
13
99
99
13
10
99
97
98
93
96
93
CpMn(CO)2ST
ССl4
–
25
50
ССl4
–
80
25
3
14
50
CpMn(CO)2MMA
ССl4
–
–
–
ССl4
–
60
10
15
3
428
754
244
679
117
498
3.0
2.7
2.2
2.5
2.2
2.4
ССl4
–
80
16
ССl4
–
100
0.7
2.5
in the initiating performance of the systems based on
the metal complexes under consideration. At 80°C, the
polymerization occurs at a high rate, and deep conversion
is attained within 3 h. In contrast to the system based
on CTM and ССl4, the MMA polymerization with the
monomer-containing complexes occurs within a shorter
time, and М and the polydispersity coefficient of the
synthesized PMMA are considerably lower. When
comparing the features of MMA polymerization in the
presence of the above metal complexes and ССl4, it
should be noted that the kind of the monomeric ligand
does not appreciably affect the polymerization rate. The
molecular-weight characteristics of PMMA synthesized
in the presence of the manganese complexes under
consideration are also comparable.
autoacceleration both in the presence of ССl4 and without
it (Fig. 1). Our results show that the chosen monomer-
containing complexes, in contrast to the known ATRP
metal complex catalytic systems [1], irreversibly react
with ССl4, generating the initiating radicals.
The PMMA samples prepared in the presence of bi-
nary initiating systems based on manganese complexes
and ССl4 at 80–100°С are characterized by a slight
increase in М with the conversion, irrespective of the
ligand surrounding of the metal complex (Table 2),
but have relatively broad MWD. The MWD curves are
unimodal and are not appreciably shifted toward higher
М values with the conversion, which confirms that only
one polymerization mechanism is realized in the system.
Similar trends are observed with ST polymerization
in the presence of the binary initiating systems.
Based on the data obtained, we chose the optimal
temperature interval for the process (80–100°С), which
is well consistent with published data on polymerization
of vinyl monomers in the presence of carbonyl complexes
of transition metals [19].
Thus, the binary compositions based on manganese
olefin complexes and CCl4 are very active initiating sys-
tems in MMAand ST polymerization, but, irrespective of
the ligand surrounding of the manganese atom, the pro-
cess occurs in the uncontrolled mode. Taking into account
the results of our experiments and the published data
[20] on the reactivity of manganese carbonyl complexes
toward halogenated organic compounds, we can suggest
A study of the MMA polymerization in the pres-
ence of the monomer-containing manganese complex
CpMn(CO)2MMA and CCl4 in the chosen temperature
interval showed that the process occurs with pronounced
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

1816
PAVLOVSKAYA et al.
Table 2. Molecular-weight characteristics of PMMA synthesized in the presence of manganese cyclopentadienyl complexes
(0.125 mol %) and various halogenated organic coinitiators (0.25 mol %)
Coinitiator
CCl4
Т, °С
τ, h
Conversion, %
Mn × 10–3
Mw/Mn
CpMn(CO)2 ST
80
80
80
0.5
1.0
2.0
13
22
46
122
144
202
2.8
2.6
–
80
80
3.0
0.5
95
18
237
141
2.6
2.3
EIB-Br
80
80
1.0
2.0
23
55
182
230
2.1
–
80
80
3.0
2.0
94
6
249
319
2.4
2.6
i-C5H11I
80
80
80
5.0
15.3
21.3
15
42
96
370
435
431
3.1
3.2
3.4
CpMn(CO)2 ММА
CCl4
80
80
80
1.0
1.5
2.0
19
34
50
195
196
223
2.1
2.1
2.1
80
100
3.0
0.3
98
24
225
113
2.3
2.0
100
100
0.5
0.6
38
61
112
114
2.2
2.2
100
100
0.8
0.3
92
28
132
80
2.1
2.2
EIB-Br
100
100
0.5
0.7
42
70
90
91
2.3
2.5
i-C5H11I
100
100
100
1.0
1.9
5.5
12
21
95
247
329
320
2.5
2.2
2.8
the following scheme for the polymerization initiation
in the presence of a halogenated compound (Scheme 2).
As follows from Scheme 2, one of the key steps of
the initiation in the systems is the interaction of the man-
Scheme 2.
Mn
CCl4
+
Mn
Mn
+ CCl3 ,
_L
OC
OC
OC
Cl
Cl CCl3
CCl3
L
OC
OC
OC
CCl3 + nM
(M) 1 M ,
_
n
n–1
M is a monomer and L is a ligand.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

MONOMER-CONTAINING MANGANESE COMPLEXES
(a) (b)
1817
τ, min
Fig. 1. Differential curves of MMA polymerization on the complex CpMn(CO)2MMA (0.125 mol %). (Vp) Polymerization rate and (τ)
time. Т, °С: (a) 80 and (b) 100. (1) With CCl4 (0.25 mol %) and (2) without CCl4.
ganese complex with a halogenated compound with the
formation of a metal–halogen bond in the metal complex.
In this connection, it was interesting to examine how the
kind of the halogen affects the performance of binary
initiating systems CpMn(CO)2L + RX (where L is the
coordinated monomer).
with i-C5H11I used as coinitiator (Fig. 2). This feature of
the iodine-containing initiator is due to its lower activity
in the polymerization initiation, probably caused by the
occurrence of the above-mentioned side reactions.
In addition, with all the initiating systems based on the
monomer-containing complexes and halogenated organic
compounds, the molecular weight of the polymers only
slightly increases with the conversion (Fig. 2), which is
consistent with the published data on their activity as
chain-transfer agents [18].
For this purpose, we chose a series of halogenated
organic compounds (RX) of different structures: CCl4,
EIB-Br, and i-C5H11I. According to published data, the
energy of the R–Х bond decreases in the order R–Cl >
R–Br > R–I; hence, the iodine-containing initiators should
be the most active radical generators [21]. However, ac-
cording to our data on the conversion, the most effective
coinitiators are CCl4 and EIB-Br (Table 2). The time in
which the deep conversion is attained in the presence of
these compounds is comparable in the case of both MMA
and ST (Table 2). Isoamyl iodide is somewhat inferior to
them in the activity. This fact can be attributed, first, to
the photosensitivity of iodine initiators and, second, to
the possibility of formation of unstable metal complexes.
In addition, alkyl iodides can undergo heterolytic decom-
position, which can give rise to a series of side reactions
and, as a result, can lead to a decrease in the performance
of these initiators, compared to the chlorinated and bro-
minated compounds [22, 23].
Thus, the experimental results show that the manga-
nese complexes containing the coordinated monomer as
one of the ligands equally actively initiate the polymer-
ization of both ST and MMA and appreciably affect the
P, %
Comparison of the molecular-weight characteristics
of PST and PMMA samples synthesized in the presence
of the chosen halogenated compounds shows that the
polymers with higher М and Mw/Mn values are formed
Fig. 2. Number-average molecular weight Мn as a func-
tion of conversion P for PST synthesized in the presence of
CpMn(CO)2ST (0.125 mol %) and (1) CCl4, (2) EIB-Br, and
(3) i-C5H11I (0.25 mol %) at 80°С.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

1818
PAVLOVSKAYA et al.
Scheme 3.
Mt _
Mt
Mt+
C
C
C
C
C
C
Mt
_
C
+ C
η2 Coordination
η1 Coordination
molecular-weight characteristics of the polymers formed.
It was interesting to study the initiating power of
η2-coordinated manganese cyclopentadienyl complexes
in polymerization of ST and MMA in the absence of
a halogen-containing initiator.
According to published data, in the course of initiation,
metal carbonyls are capable, though to a small extent,
to form η2 complexes with monomers [24], which can
subsequently rearrange to form reactive species accord-
ing to the Scheme 3.
We found that the metal complexes under consider-
ation, in contrast to cymantrene which, as noted above,
inhibits thermal radical polymerization of MMA [17],
appeared to be capable to initiate the MMA and ST po-
lymerization in a relatively wide temperature interval,
from 25 to 100°С (Table 1). The molecular weight of the
PMMA samples synthesized in the presence of the man-
ganese complexes appeared to be somewhat higher than
that of the polymers obtained with ССl4 as coinitiator.
Table 3. Molecular-weight characteristics of PST and PMMA
synthesized in the presence of various manganese cyclopen-
tadienyl complexes (0.125 mol %)
Conversion,
Polymer Т, °С
τ, h
Mn × 10–3 Mw/Mn
%
CpMn(CO)2 ST
Analysis of the specific features of the polymer syn-
thesis on monomer-containing manganese complexes
showed that the MMA polymerization in the presence of
CpMn(CO)2MMAtakes longer time than with the binary
initiating system (Table 3). The MMA polymerization
occurs with autoacceleration at deep conversions, but,
in contrast to the CpMn(CO)2MMA + ССl4 system, the
gel effect is less pronounced. As in the case of the initia-
tion with the binary system, the ST and MMA polym-
erization initiated with the manganese complexes taken
alone occurs at these temperatures to deep conversions
irrespective of the kind of the monomeric ligand. As
seen from Fig. 3, the rate of the ST polymerization under
comparable conditions is slightly higher when using the
monomer-containing complex with a like ligand, ST,
compared to the complex CpMn(CO)2MMA. The com-
plex CpMn(CO)2SТ exhibits higher catalytic activity in
ST polymerization and does so at lower temperatures. Its
initiating power is comparable with that of the classical
radical initiators, e.g., azobis(isobutyronitrile) (AIBN)
and peroxides [18].
PST
80
80
80
80
80
80
80
80
80
6.0
15.0
28.0
33.0
40.0
3.0
7
15
26
59
78
12
18
25
96
156
221
233
231
230
259
278
340
–
3.3
2.5
2.1
2.3
2.5
4.2
4.3
3.8
–
PMMA
5.0
6.0
14.0
CpMn(CO)2 ММА
PMMA
PST
100
100
100
100
100
100
100
100
100
0.5
2.0
6
25
41
95
15
24
30
40
81
368
382
480
498
221
233
257
277
320
2.4
2.5
2.3
2.4
1.9
2.1
1.9
1.9
2.3
2.3
3.0
2.0
5.0
The PMMAand PST samples synthesized in the pres-
ence of the metal complexes are characterized by rela-
tively broad molecular-weight distribution. The MWD
curves are not noticeably shifted toward higher molecular
weights with an increase in the monomer conversion.
12.0
13.0
20.0
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

MONOMER-CONTAINING MANGANESE COMPLEXES
1819
Scheme 4.
O
C
Mn
H2C
OC
OCH3
C
CH3
OC
Mn
CO
+ MMA
OC
OC
CH3
C
CH3
C
Mn
CO
Mn
CO
CH2
+ nMMA
CH2
OC
O
O
C
C
n
OCH3
OCH3
The polydispersity coefficients of the synthesized poly-
mers (Table 3) exceed 2.0, which indicates that, with the
monomer-containing manganese complexes, the MWD
of the polymers is not controlled to sufficient extent.
of the synthesized polymers.
In addition, from the 1H NMR data for PMMA syn-
thesized in the presence of the monomer-containing
manganese complexes we determined the ratio of syn-
Thus, we found experimentally that the manganese
complexes containing a π-bonded olefin ligand (MMA
or ST) are capable to initiate the polymerization
of vinyl monomers in a wide temperature interval
(25–100°C) even when taken alone (without halogenated
coinitiator).
P, %
The experimental data obtained, in combination with
the published data [24], allow us to suggest the follow-
ing scheme of the MMA and ST polymerization in the
presence of manganese complexes:
Scheme 2 is well consistent with the results of quan-
tum-chemical simulation of the possible reactions involv-
ing monomer-containing manganese complexes [13].
To prove the radical nature of the initiation, we per-
formed the MMA polymerization in the presence of the
manganese complexes and 2,2,6,6-tetramethylpiperidine-
1-oxyl (TEMPO) as stable nitroxyl radical capable to
inhibit radical polymerization [25]. We found that in-
troduction of 0.25 mol % TEMPO into the system fully
inhibits the MMA polymerization at 80 and 100°С. On
the contrary, introduction of acetonitrile (CH3CN) used
as inhibitor of anionic polymerization affects neither the
polymer yield nor the molecular-weight characteristics
τ, h
Fig. 3. Polymerization of ST in the presence of manganese
complexes (0.125 mol %). (Р) Conversion and (τ) time. (1, 3)
CpMn(CO)2ST and (2) CpMn(CO)2ММА. T, °С: (1, 2) 100
and (3) 80.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 10 2011

1820
PAVLOVSKAYA et al.
6. Ziegler, K., Adv. Organomet. Chem., 1968, vol. 6, no. 1,
diotactic, heterotactic, and isotactic triads in the samples
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pp. 1–17.
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CONCLUSIONS
9. Sinn, H., Kaminsky, W., Vollmer, Y.-J., and Woldt, R.,
Angew. Chem. Int. Ed., 1980, vol. 19, no. 5, pp. 390–392.
(1) The manganese complexes containing a π-bonded
olefin ligand are capable to initiate the polymerization of
styrene and methyl methacrylate in a wide temperature
interval (25–100°С). The kind of the olefin ligand does
not appreciably affect the polymerization rate of the vinyl
monomers and the molecular-weight characteristics of
the samples synthesized.
10. Choi, S.-K., Gal, Y.-S., Jin, S.-H., and Kim, H.K., Chem.
Rev., 2000, vol. 100, no. 4, pp. 1645–1681.
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464.
(2) Introduction of a halogenated organic derivative
into the system leads to the process acceleration and to
a decrease in the molecular weight of the polymers syn-
thesized in the presence of the monomer-containing man-
ganese complexes, which indicates that the halogenated
organic compound directly participates in elementary
steps of the polymerization.
14. Angelici, R.J. and Loewen, W., Inorg. Chem., 1967, vol. 6,
no. 4, pp. 682–686.
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ACKNOWLEDGMENTS
The authors are grateful to N.A. Ustynyuk and
V.V. Krivykh (Nesmeyanov Institute of Organoelement
Compounds, Russian Academy of Sciences) for useful
discussions and for submission of the monomer-contain-
ing manganese complexes.
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pp. 1024–1028.
The study was financially supported by theAnalytical
Target Program “Development of the Scientific Potential
of Higher School” and by the Russian Foundation for
Basic Research (project no. 11-03-00074).
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