Controlled polymerization of styrene in the presence of Blatter’s radicals

Article abstract of DOI:10.1007/s11172-020-2925-1

Controlled polymerization of styrene (both self-initiated and initiated with azobisisobutyronitrile) in the presence of Blatter’s radical at 125 °C was studied. When using the radical initiator, there is no induction period. On the basis of UV spectroscopy and MALDI massspectrometry studies, it was established that the Blatter radical is completely consumed at the initial stage of the polymerization, inserting into almost all macromolecules. The prepared polystyrene exhibits the ability to reinitialization in post-polymerization and the synthesis of block copolymers.

Full text of DOI:10.1007/s11172-020-2925-1

Russian Chemical Bulletin, International Edition, Vol. 69, No. 8, pp. 1470—1477, August, 2020
1470
Controlled polymerization of styrene
in the presence of Blatter´s radicals
Yu. L. Kuznetsova,a A. S. Vavilova,a Yu. B. Malysheva,a M. A. Lopatin,b I. D. Grishin,a
T. O. Burdyukova,a E. A. Zaburdaeva,a E. Yu. Polozov,a A. Yu. Fedorova
aNational Research Lobachevsky State University of Nizhni Novgorod,
23 prosp. Gagarina, 603950 Nizhni Novgorod, Russian Federation.
Fax: +7 (831) 462 3085. E-mail: kyul@yandex.ru
bRazuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,
49 ul. Tropinina, 603137 Nizhni Novgorod, Russian Federation.
Fax: +7 (831) 462 7497
Controlled polymerization of styrene (both self-initiated and initiated with azobisiso-
butyronitrile) in the presence of Blatter´s radical at 125 С was studied. When using the radical
initiator, there is no induction period. On the basis of UV spectroscopy and MALDI mass-
spectrometry studies, it was established that the Blatter radical is completely consumed at the
initial stage of the polymerization, inserting into almost all macromolecules. The prepared
polystyrene exhibits the ability to reinitialization in post-polymerization and the synthesis of
block copolymers.
Key words: styrene, Blatter´s radical, controlled radical polymerization, reversible inhibi-
tion, macroinitiator, post-polymerization, block copolymer.
Controlled radical polymerization (CRP) considerably
simplifies the problem of the structural control of formed
polymers and makes it possible to obtain polymers with
precisely controlled molecular structure. One of the CPR
mechanisms is the mechanism with a reversible inhibition
with participation of stable radicals, viz., the stable free
radical polymerization, SFRP. This type of CRP was
discovered quite a long time ago,1,2 but remains relevant
today.3—5 The SFRP process can be represented as shown
in Scheme 1.
mainly because of their magnetic properties and ability to
form semiconducting, pressure sensitive charge transfer
complexes with tetracyanoquinodimethane. Only a few
studies were devoted to polymerization in the presence of
Blatter´s radicals.21,26 The first of them21 considered
styrene polymerization in the presence of Blatter´s radicals
bearing different substituents for the first time.
Scheme 1
R = H, CF3, I, Br, Cl, Ph, fur-2-yl-, 4-PhC6H4
It was shown that the formed polystyrene (PS) was
characterized by a polydispersity index of 1.05—1.27,
however the monomer conversion did not exceed 21.2%.
Polymerization of styrene in the presence of two Blatter´s
radicals (R = H, Ph) proceeds according to the SFRP
mechanism (see scheme 1), however the GPC data indi-
cate the presence in the system of a significant proportion
of a dead polymer, which limits the practical value of such
polymer products. In the second study,26 it was suggested
to increase the monomer conversion by using an iniferter,
decomposition of which produces both initiating and
inhibiting radicals. We believe that the use of a radical
initiator in combination with Blatter´s radical can have
R• is a chain propagation radical; •X is a stable radical;
M is a monomer.
SFRP in the presence of a series of stable radicals such
as triarylmethyl and related radicals,6—8 phenoxyl,9—12
nitroxyl,13—16 and boroxyl radicals3,4,17—20 or in the pres-
ence of their precursors is well studied. Stable radicals can
be either introduced into the reaction mixture,14,15,21 or
generated in situ.10—13,17—20 A wide variety of monomers
can be used in this process.
Lately, a number of studies21—25 devoted to Blatter´s
radicals were reported. These radicals are interesting
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1470—1477, August, 2020.
1066-5285/20/6908-1470 © 2020 Springer Science+Business Media LLC

Controlled polymerization of styrene
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1471
2 h. Pink crystals of N,N´-diphenyl benzohydrazone amide (III)
(2.2 mmol, 36%) were obtained. At the last step,26 compound
III (1.1 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU,
0.11 mmol), and palladium on carbon (Pd/C, 0.017 mmol) were
dissolved in methylene chloride (2.2 mL). The reaction mixture
was stirred at 20 С for 3 h. BR (0.9 mmol, 82%) was obtained
in the form of air-stable black needle-shaped crystals. BR was
characterized using MALDI-TOF mass spectrometry, UV, IR,
and ESR spectroscopies.31
The purity of all used compounds was verified using NMR
spectroscopy. The 1Н and 13С NMR spectra were recorded in
CDCl3 using an Agilent DD2 400 NB spectrometer with operat-
ing frequencies of 400 and 101 MHz, respectively.
an effect similar to the use of an iniferter since it should
reduce the inhibiting effect of the stable radical and,
therefore, significantly increase the monomer conversion.
This study is devoted to the investigation of the styrene
polymerization initiated by azobisisobutyronitrile (AIBN)
in the presence of Blatter´s radical (BR), viz., 1,4-dihydro-
1,3-diphenyl-1,2,4-benzotriazine-4-yl, as well as to an
analysis of formed PS using GPC, UV spectroscopy, and
MALDI-TOF mass spectrometry, to exploration of abil-
ity of formed PS to reinitialization, and to comparison of
these results with those obtained for self-initiated styrene
polymerization.
To carry out polymerization, a solution of BR (or BR and
AIBN) in styrene was placed in an ampoule and degased three
times using a freezing-thaw procedure at reduced pressure. The
ampoule was sealed and placed in a thermostat heated to 125 С.
The styrene conversion was determined gravimetrically. Post-
polymerization was carried out with PS obtained at conversions
of 28—42%, which was twice re-precipitated from chloroform
to isopropyl alcohol and dried. A 5% solution of polystyrene in
styrene was used. Solutions of a macroinitiator (MI) in styrene
were heated at 125 С for 2 and 4 h. The synthesis of block co-
polymer of styrene and methyl methacrylate (PS-b-PMMA) was
carried out analogously for 0.5 and 1 h.
Molecular weight distribution characteristics of obtained
polymers were obtained using GPC in THF at 40 С with the
use of a Shimadzu liquid chromatograph equipped with columns
filled with polystyrene gel with pore sizes of 1•106 and 1•105 Å.
A differential refractometer was used as a detector. Chromato-
grams were processed using the LCsolution software. Narrowly
dispersed PS standards were used for calibration.
UV spectra of solutions of BR and PS in chloroform were
recorded using a Shimadzu UV-1800 spectrometer. MALDI-TOF
mass spectra of polymers were obtained with the use of a Bruker
Microflex LT mass spectrometer. Matrix substance for MALDI-
MS was trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenyl-
idene]malononitrile, a cationizing agent was silver acetate. The
sample was prepared by mixing solutions of polymer, matrix, and
cationizing agent (5 : 25 : 1) in THF and applying the resulting
Experimental
Organic solvents were purified according to known proce-
dures.27 Styrene and methyl methacrylate (MMA) were washed
from an inhibitor with a 10% alkali solution and, then, with
distilled water to a neutral reaction, dried over anhydrous so-
dium sulfate, and distilled at 52—54 С (at 4.3 kPa) in the case
of styrene and at 25 С (at 2.93 kPa) in the case of MMA.28
Azobisisobutyronitrile (Reachem, RF) was recrystallized from
diethyl ether and dried to constant weight.
Blatter´s radical was obtained according to Scheme 2. At the
first step,29 phenylhidrazine (0.049 mol) was dissolved in pyridine
(39 mL), and benzoyl chloride (0.049 mol) was added. The reac-
tion mixture was stirred at ~20 °C for 48 h. N´-phenyl benzo-
hydrazide (I) (0.027 mol, 55%) was obtained in the form of
colorless lamellar crystals. At the second step,29 compound I
(0.025 mol) and phosphorus pentachloride (0.0275 mol) were
boiled in carbon tetrachloride (72 mL) under stirring for 3 h.
Then, solution of phenol (0.13 mol) in carbon tetrachloride
(36 mL) was added. The reaction mixture was stirred at 0 С for 1 h.
Colorless crystals of N´-phenyl benzohydrazonoyl chloride (II)
(0.008 mol, 32%) were obtained. At the third step,30 compound
II (6 mmol) was dissolved in ethanol (3 mL), aniline (6.0 mmol)
and a solution of triethylamine (7.1 mmol) in ethanol (1.5 mL)
were added. The reaction mixture was boiled under stiring for
Scheme 2
Reagents and conditions: i. 1) PCl5, CCl4; 2) PhOH, CCl4; ii. PhNH2, Et3N, EtOH; iii. 0.1 eq. DBU, 1.6 mol.% Pd/C, CH2Cl2.

Kuznetsova et al.
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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
solutions to a stainless steel plate. Narrowly dispersed standards
based on PS were used for calibration of the spectrometer.
curve 3). Introduction of BR together with AIBN (see
Fig. 1, b, curves 1—3) results in the disappearance of the
inductive period and, in the presence of the 0.1 mol.%
inhibitor, makes it possible to achieve high conversions
(see Fig. 1, b, curve 3). The styrene polymerization rate
in the presence of 0.4 mol.% BR (see Fig. 1, b, curve 1) is
higher than in the presence of 0.25 mol.% BR (see Fig. 1, b,
curve 2) similarly to the case of self-initiated polymeriza-
tion (see Fig. 1, а, curves 1 and 2). It can be supposed that
the use of a radical initiator increases the concentration of
initiating radicals in comparison with the self-initiated poly-
merization, which reduces the inhibiting action of BR.
Thus, the changes in the polymerization kinetics due
to variations in the BR and AIBN concentrations charac-
terize BR as a weak inhibitor.
Results and Discussion
Self-initiated styrene polymerization in the presence
of 0.4 mol.% BRs of different composition was already
considered in study21 where the PS synthesis was carried
out in a round bottom flask at 125 С under the nitrogen
atmosphere. Conversion was determined gravimetrically.21
In the present study, the synthesis of polystyrene at 125 С
in the presence of 0.4 mol.% BR was performed in evacu-
ated ampoules (Fig. 1, а, curve 1). Note that a decrease
in the BR concentration (see Fig. 1, а, curve 2) reduces
the polymerization rate and lengthens the induction period.
Styrene polymerization initiated by 0.1 mol.% AIBN
is characterized by a higher rate (see Fig. 1, b, curve 4) as
compared to self-initiated polymerization (see Fig. 1, а,
All PS samples prepared at different BR concentrations
in the presence or absence of AIBN have number average
molecular weights (Mn) lower (Figs. 2 and 3) than those
P (%)
100
P (%)
100
a
b
4
3
3
80
60
40
20
80
60
40
20
1
2
1
2
4
8
12
t/h
4
8
12
t/h
Fig. 1. Kinetics of styrene polymerization at 125 С without initiator (а) in the presence of BR in concentrations of 0.4 (1), 0.25 mol.% (2),
and without BR (3) and with 0.1 mol.% AIBN as an initiator (b) in the presence of BR in concentrations of 0.4 (1), 0.25 (2),
0.1 mol.% (3), and without BR (4).
a
b
2
1
2
3
1
3
4
3
4
5
lgM
3
4
5
lgM
Fig. 2. Evolution of MMD for PS synthesized in the presence of 0.4 mol.% BR (а) at conversions of 6.3% (1), 18.7% (2), and 28.6% (3)
and 0.25 mol.% BR (b) at conversions of 4.6% (1), 12.5% (2), 21.9% (3), and 28.8% (4).

Controlled polymerization of styrene
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1473
2
3
2
2
a
b
c
1
3
1
4
1
3
3
4
5
lgM
3
4
5
lgM
3
4
5
lgM
Fig. 3. Evolution of MMD for PS synthesized in the presence of 0.4 mol.% BR and 0.1 mol.% AIBN (а) at conversions of 10.3% (1),
15.5% (2), 19.8% (3), and 38.5% (4), in the presence of 0.25 mol.% BR and 0.1 mol.% AIBN (b) at conversions of 9.5% (1), 16.6% (2),
and 31.1% (3), and in the presence of 0.1 mol.% BR and 0.1 mol.% AIBN (c) at conversions of 22.5% (1), 41.8% (2), and 74.2% (3).
of polymers prepared in the absence of the inhibitor. The
number average molecular weights are 170000 in the case
of self-initiated styrene polymerization and 70000 in the
case of the AIBN initiated polymerization; the polydis-
persity index is in the range 1.1—1.5. There is a tendency
to narrowing the dispersion of the Mn values.
The molecular mass distribution (MMD) curves shown
in Figs. 2 and 3 correspond to regularities typical of the
SFRP processes (Scheme 3), however, in all the cases,
a low-molecular fraction is retained, which was attributed21 to
the presence of a certain fraction of dead polymer. Growth
of Mn is proportional to the increase in the transformation
depth (Fig. 4), which is typical of SFRP. However, this
dependence does not pass through the origin of coordi-
nates. This is due to the fact that the occurrence of CRP
requires formation of an oligomeric adduct between
radical propagating the chain and BR. This adduct plays
a role of MI (see Scheme 3).
favors formation of larger amount of MI and, therefore,
the increase in the process rate.
The fact of embedding BR into the polymer chain was
confirmed using UV spectroscopy (Fig. 5). The absorption
bands at 271, 322, 372, 429, and 494 nm are present in the
UV spectrum of free BR (see Fig. 5, curve 1).31 The UV
spectrum of PS (see Fig. 5, curve 2) prepared in the pres-
ence of BR has the same absorption bands, although, with
considerably changed relative intensities. Thus, the elec-
tronic transitions determining the appearance of the bands
at 322, 372, 429, and 494 nm remain unchanged for both
free BR and BR included into the polymer chain. However,
the extinction coefficients of these bands are determined
by the probabilities of the corresponding electronic tran-
sitions, depending on the difference in polarizability of
the ground and excited states. Therefore, the absorption
band intensities should depend on the surroundings of the
chromophore. Indeed, the relative intensities of these
Scheme 3
Mn•10–4
5
4
5
3
4
3
2
1
2
1
20
40
60
80 P (%)
In accordance with Scheme 3, the higher the concen-
tration of starting BR, the higher the amount of MI formed.
We believe that the increase in the BR concentration from
0.25 to 0.4 mol.% (see Fig. 1, curves 2 and 1, respectively)
Fig. 4. Dependence of Mn on the conversion of PS samples
prepared at 125 С in the presence of BR in concentration of 0.4 (1)
and 0.25 mol.% (2) and in the presence of 0.1 mol.% AIBN and
BR in concentrations of 0.4 (3), 0.25 (4), and 0.1 mol.% (5).

Kuznetsova et al.
1474
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
D
in our case. The UV spectrum of the mother liquor after
precipitation of the polymer (see Fig. 5, curve 3) contains
absorption bands in the region 250—280 nm, which belong
to phenyl groups of oligomeric PS. Thus, all BR molecules
are incorporated into the polymer chain already at the
10% conversion of the monomer.
4
2
2
1
Thus, all obtained experimental data indicate BR
embedding into the polymer chain. However, the UV data
do not answer the question if all chains contain BRs. To
answer this question, a MALDI-TOF mass spectrometry
study was carried out. A mass spectrum typical of all ob-
tained polymers is shown in Fig. 6. Two main series of
peaks differing by 104 Da, which corresponds to a styrene
moiety, are seen in the spectrum. A peak at 3273.0 Da
corresponds to a macrocation of a dormant chain, consist-
ing of an AIBN residue, 27 links of styrene, BR, and silver
cation (calculated value is 3272.3).
3
350
450
550 /nm
Fig. 5. UV spectra of chloroform solutions of BR (1), PS prepared
by styrene polymerization in the presence of 0.25 mol.% BR at
the 12.5% conversion (2), and mother liquor after precipitation
of PS (3).
bands are different in the spectra of free and embedded
BR, and this difference is stronger in the short-wavelength
region because of the mentioned influence of the reaction
center. The changes occurring with the band at 271 nm
require a separate consideration. This band is the benzene
fragment band (1Lb according to the Platt notation), which
is responsible for the transitions within the benzene ring.
Substitution in the ring results in its bathochromic shift.
The simultaneous presence of substituents of several types
leads to the broadening of this band or to the appearance
of a complex structure for it. The latter effect was observed
Macrocation
This observation of this peak confirms that the revers-
ible inhibition due to addition of BR to growing chains
takes place.
3315.6
3211.5
3420.0
3376.3
3273.0
3200
3300
3400
m/z
2000
3000
4000
5000
m/z
Fig. 6. MALDI-TOF MS of PS prepared at 125 С in the presence of 0.1 mol.% AIBN and 0.25 mol.% BR; the inset shows an enlarged
relevant part of the spectrum.

Controlled polymerization of styrene
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1475
Table 1. Characteristics of MIs obtained by styrene polymerization at 125 С in the presence of BR
MI
Initiator of the styrene polymerization
Р (%)
Мn•10–3 Мw•10–3
Мw/Мn
I
BR (0.4 mol.%)
30.1
28.8
32.2
41.8
17
23
25
42
25
34
33
48
1.49
1.46
1.32
1.15
II
III
IV
BR (0.25 mol.%)
AIBN (0.1 mol.%), BR (0.25 mol.%)
AIBN (0.1 mol.%), BR (0.1 mol.%)
Scheme 4
The most intensive series of peaks in the mass spectrum
(3211.5 and subsequent), apparently, corresponds to
a product of fragmentation of BR moiety under the
analysis conditions. Presumably, the fragmentation pro-
ceeds according to the pathway shown in Scheme 4 and
results in the formation of macrocations containing an
amino group at the end of the chain.
Similar fragmentation processes in mass spectrometry are
well known for substituted imidazoles.32 The calculated m/z
value for the final cation consisting of an AIBN residue,
29 styrene links, an amino group, and silver cation is 3211.3,
it well corresponds to the m/z value observed in the spectrum.
Thus, the conducted mass spectrometric study of the
obtained samples showed that the predominant part of the
formed polymer chains contain BR at their ends, while
the proportion of dead polymer is insignificant.
One of the main characteristics of the controlled poly-
merization is the ability of the formed polymers to continue
the process when a new portion of the monomer is added.
Post-polymerization was carried out with PS samples
whose characteristics and designations are given in Table 1.
All used MIs (see Table 1) exhibit the ability to reini-
tialization, which is evidenced by the increase in conver-
sion and Mn (Table 2). The maxima on the MMD curves
for the post-polymers are displaced to higher Mn values
(Fig. 7, curves 2 and 3) in comparison with those of the
MMD curves for MIs (see Fig. 7, curve 1).
Yields and Mn values tend to increase with the decrease
in the BR concentration in MI (see Table 2). Polydispersity
of post-polymers in comparison with MIs increases (see
Table 2) due to incomplete consumption of the latter (see
Fig. 7, curves 2 and 3). However, MMD becomes narrower
with the increase in the transformation depth except the
case of MI IV. Probably, the fraction of dead polymer is
high in the latter case, which can be related to the low
content of BR in this MI.
The capability of PS obtained in the presence of BR
to reinitialization was also studied in the synthesis of block
copolymer PS-b-PMMA. In particular, MI IV (see Table
1) produces PS-b-PMMA as it follows from changes in
Mn and MMD (Table 3, Fig. 8).
In the course of synthesis of PS-b-PMMA, MMD
acquires a bimodal character (see Fig. 8, curves 2 and 3).
The low-molecular mode corresponds to MI IV (see Fig. 8,
curve 1), and the high-molecular one conforms with the
block copolymer. With the increase in the transformation
depth, the low-molecular mode decreases, while the high-
molecular mode increases and becomes displaced to higher
Mn. The obtained polymer cannot be a product of thermal
polymerization of MMA since its Mn is an order of mag-
nitude higher (see Fig. 8, curve 4).
On the whole, we established that the self-initiated
polymerization of styrene in the presence of BR proceeds
according to the SFRP mechanism (see Scheme 3) and is
accompanied by an induction period,21 during which MI
is formed. In the presence of AIBN, a radical initiator,
there is no induction period, whereas the mechanism
remains the same. In all the cases, BR is completely in-
Table 2. Data on post-polymerization of styrene at 125 С in the
presence of 5 wt.% MI (P0 = 4.8%)
MI
t/h
P (%) Р/Р0 Mn•10–3 Mw•10–3 Мw/Мn
I
2
4
23.6
43.0
19.1
46.9
37.8
44.5
36.3
47.4
4.9
9.0
4.0
9.8
7.9
9.3
7.6
9.9
84
109
92
132
87
110
107
122
146
183
209
283
173
220
180
250
1.73
1.68
2.27
2.14
2.00
2.00
1.68
2.05
II
2
4
2.67
4
2
4
III
IV

Kuznetsova et al.
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Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
3
3
a
b
2
2
1
1
4
4
3
4
5
6
7
lgM
3
4
5
6
7
8
lgM
3
4
c
d
3
2
2
1
1
4
3
4
5
6
7
8
lgM
3
4
5
6
7
lgM
Fig. 7. MMD for MI I (а), MI II (b), MI III (c), and MI IV (d) (curves 1) and post-polymers obtained for 2 (2) and 4 h (3), as well
as of PS synthesized in the absence of MI (4).
1
2
3
4
3
4
5
6
7
lgM
Fig. 8. MMD for MI IV (1) and PS-b-PMMA prepared for 0.5 (2) and 1 h (3), as well as for PMMA synthesized without addition of
MI (4).
cluded in the polymer chain as it was confirmed by the
Table 3. Data on synthesis of PS-b-PMMA at 125 С in the
UV data. At the same time, according to the MALDI-TOF
mass spectrometry data, almost all polymer chains contain
BR moieties at their ends. This indicates only an insig-
nificant fraction of dead polymer. The obtained samples of
PS actively participate in the processes of reinitialization,
post-polymerization, and synthesis of block copolymers.
presence of 5 wt.% MI IV (P0 = 4.8%)
t/h
P (%)
Р/Р0
Mn•10–3 Mw•10–3 Мw/Мn
0.5
1.0
9.3
12.3
1.9
2.6
58
63
97
174
1.66
1.80

Controlled polymerization of styrene
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 8, August, 2020
1477
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Received September 30, 2019;
in revised form January30, 2020;
accepted March 15, 2020