Advanced approaches in radiation-chemical synthesis of phosphorus- containing polymers

Article abstract of DOI:10.1016/j.crci.2010.05.013

The transition from micro- to nanoscale systems brings major changes to the basic physicochemical properties of polymers. The polymers of elemental phosphorus (phosphorus-containing polymers [PCPs]) display this phenomenon, for example, in magnification of reactivity, changes of self-ignition temperature and of other critical technological characteristics. It determined our special attention to the progress of synthesis technology of nanoscale inorganic polymers with the tailor-made properties. At the heart of the technology designed, there are principles of green chemistry which allow us to take into account the current trends in inorganic synthesis, in particular, the usage of ionizing radiation and varying of media properties for the nanoscale particle growth control. This type of the process control allowed us to move from the acting principle of physicochemical investigations composition- properties to a principle synthesis conditions-composition- properties . The control by means of varying media properties may be realized by different approaches: variation of the solvent nature (limitation on solubility of phosphorus in different solvents) and variation of media polarity and the structural organization of the solution (incorporation of ionic liquids [ILs] into the reaction media).

Full text of DOI:10.1016/j.crci.2010.05.013

C. R. Chimie 13 (2010) 1028–1034
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´
Full paper/Memoire
Advanced approaches in radiation-chemical synthesis of phosphorus-
containing polymers
*
Natalia P. Tarasova, Alexey A. Zanin , Yury V. Smetannikov, Alexander S. Vilesov
D. Mendeleyev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, Russia
A B S T R A C T
A R T I C L E I N F O
Article history:
The transition from micro- to nanoscale systems brings major changes to the basic
physicochemical properties of polymers. The polymers of elemental phosphorus
(phosphorus-containing polymers [PCPs]) display this phenomenon, for example, in
magnification of reactivity, changes of self-ignition temperature and of other critical
technological characteristics. It determined our special attention to the progress of
synthesis technology of nanoscale inorganic polymers with the tailor-made properties. At
the heart of the technology designed, there are principles of ‘‘green’’ chemistry which
allow us to take into account the current trends in inorganic synthesis, in particular, the
usage of ionizing radiation and varying of media properties for the nanoscale particle
growth control. This type of the process control allowed us to move from the acting
principle of physicochemical investigations ‘‘composition–properties’’ to a principle
‘‘synthesis conditions–composition–properties’’. The control by means of varying media
properties may be realized by different approaches: variation of the solvent nature
(limitation on solubility of phosphorus in different solvents) and variation of media
polarity and the structural organization of the solution (incorporation of ionic liquids [ILs]
into the reaction media).
Received 29 January 2010
Accepted after revision 12 May 2010
Keywords:
Phosphorus-containing polymer
Radiation-induced polymerization
Elemental phosphorus
Ionic liquid
Phosphonium
ß 2010 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
1. Introduction
found that the isolated polymers contained an insignificant
amount of ionic liquids, and it is not necessary to wash
The use of ionic liquids in polymerization processes
makes it possible to enhance the activity of catalysts, to
increase selectivity, and to simplify the separation of pure
products with the repeated use of the ionic liquid and the
catalyst. In the test processes [1], the yields of target
products from low-molecular-weight oligomers to high-
molecular-weight polymers can be optimized by varying
reaction conditions (reaction time, temperature, and
catalyst structure).
them with water. The probability of further transforma-
tions (i.e., isomerization) of the polymers is low because
the process is simplified. Ionic liquids do not decompose
upon treatment with water, and they can be used
repeatedly. This reduces operational costs and is an
important advantage of ionic liquids in terms of green
chemistry.
2. Radiation-chemical synthesis of phosphorus-
containing polymers with the participation of ionic
liquids
The polymers synthesized in ionic liquids can be easily
separated and isolated in a maximally pure state. It was
Red phosphorus modifications are of considerable
interest because these inorganic polymers can be widely
used [2–4]. It is important to prepare red phosphorus
under milder conditions because of the specific proper-
ties of white phosphorus (high reactivity, fire and
* Corresponding author.
E-mail addresses: tarasnp@muctr.edu.ru (N.P. Tarasova),
alexey.zanin@gmail.com (A.A. Zanin), smetyv@muctr.edu.ru
(Y.V. Smetannikov), vilesov@gmail.com (A.S. Vilesov).
1631-0748/$ – see front matter ß 2010 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.crci.2010.05.013

N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
1029
explosion hazards, and toxicity). One of the most
interesting techniques for initiating the synthesis of
red phosphorus is a radiation-chemical technique. Its
advantages and disadvantages can be determined in
comparison with traditional thermal methods. However,
it is evident that only radiation-induced initiation makes
it possible to perform the polymerization of white
phosphorus in nonaqueous media to prepare red
phosphorus modified with solvent fragments. The
formation of red phosphorus in various systems under
the action of ionizing radiation has been studied
[4–6].
polymerization of elemental phosphorus, in comparison
with imidazolium and pyrrolidinium ionic liquids.
3. Experimental
In this study, ionic liquid [Et3OcP]NTf2–triethyloctyl-
phosphonium bis(trifluoromethylsulfonyl)imide [(C8H17
)
(C2H5)3P]+[N(SO2CF3)2]ꢀ(99.9% purity; Nippon Chemical,
Japan) was used.
White phosphorus was purified in accordance with a
modified procedure [7]. The solvents were purified using
the standard procedures [8].
Depending on the composition of the reaction mixture
and the reaction conditions, the phosphorus content of the
resulting samples can be as high as 96 wt %, the
concentration of solvent fragments can vary to 40 wt %,
and the self-ignition temperature can be 373–593 K. Based
on the experimental data, a conclusion was made that the
irradiation products were red phosphorus, a polymer
phosphorus modification.
Phosphorus-containing polymers modified with sol-
vent fragments can be synthesized by performing the
polymerization of elemental phosphorus in various
solvents and initiating systems.
PCPs were synthesized using the procedure described
below. 390 ml of benzene and 7.95 g of the elemental
(white) phosphorus were placed into the retort (1000 ml)
and stirred at ꢁ320 K until the white phosphorus was
completely dissolved. Then 13 ml of the IL was added,
while stirring, and after that 52 ml of propan-2-ol. The
mixture was cooled in a water bath to room temperature
(the solution became turbid), and filtered. The resulting
solution was placed into the hermetically sealed reactor
and irradiated using the irradiation installation MRCh-g-
100 (isotope 60Co, radiation absorbed dose rate
Dꢂ = 0.30 Gy/s, irradiation time 15.5 hours, radiation
absorbed dose D = 16.7 kGy).
Red phosphorus prepared by the
g-irradiation of a
solution of white phosphorus in benzene (henceforth, it is
referred to as a phosphorus-containing polymer (PCP))
exhibited properties comparable to those of commercial
red phosphorus samples.
The radiation-initiated polymerization of elemental
phosphorus in the presence of the following imidazolium
and pyrrolidinium ionic liquids was studied [6]: 1-butyl-3-
methylimidazoliumtriflate[BuMeIm]OTf,tetrafluoroborate
[BuMeIm]BF4, and hexafluorophosphate [BuMeIm]PF6;
The irradiated mixture presented itself as a yellowish
liquid containing a fine dispersion of an orange precipitate.
The precipitate was filtered off using a double-layered
filter paper box, and the latter was placed into the Soxhlet
apparatus, where the precipitate was washed out with
200 ml of benzene for 18 hours. After that, the washed-out
phosphorus-containing polymer was dried in the desicca-
tor under vacuum (water-jet pump) until the constant
mass value was obtained.
1-butyl-3-methylpyrrolidinium
bistriflamide
[BuMe-
The reaction products were characterized by elemen-
tal analysis, XPS data, IR spectroscopy (Bruker
Tensor 27 M instrument), X-ray diffraction analysis
(DRON-3 M diffractometer), scanning electron micros-
copy (SEM) and transmission electron microscopy (TEM)
Pyr]NTf2; and 1-hexyl-3-methylimidazolium tris(penta-
fluoroethyl)trifluorophosphate [HeMeIm](C2F5)3PF3. It
was found that the rate of radiation-initiated polymeriza-
tion of white phosphorus increased upon the addition of an
ionic liquid (Table 1).
and NMR
(
31P, 1H)-spectroscopy. The micrographs
The structure and concentration of an ionic liquid in the
system were found to affect considerably the rate of
polymerization. The introduction of an ionic liquid into the
P4–benzene–dimethyl sulfoxide (DMSO) system resulted
in a increase in the rate of reaction and an increase in the
conversion of P4; the formation of a PCP was a second-
order reaction with respect to elemental phosphorus
were taken using Tesla BS 340 scanning electron
microscope.
4. Results and discussion
The PCP prepared by the polymerization of white
phosphorus in the propan-2-ol–benzene–phosphonium
ionic liquid system (Table 2) was a finely dispersed orange
powder. It was insoluble in accessible polar and nonpolar
solvents; this is characteristic of previously described
phosphorus-containing polymers and commercial red
phosphorus [9,10].
because, hypothetically, the formation of
a complex
between the ionic liquid and P4 was a rate-limiting step
of the reaction [6].
The aim of this work was to study the effect of
phosphonium ionic liquids on the radiation-initiated
Table 1
G-values (radiation-chemical yields) of PCPs (molecule P4)/(100 eV) in the presence of ionic liquids in a DMSO–benzene mixture (1:1) (T = 298 K,
Dꢂ = 0.59 Gy/s) [6].
Ionic liquid
[BuMeIm]
OTf
[BuMeIm]
BF4
[BuMeIm]
PF6
[EtMeIm]
NTf2
[BuMePyr]
NTf2
[=eMeIm]
(C2F5)3PF3
Without ionic liquid
[P4]0/[IL]
0.075
0.072
0.069
0.215
0.081
0.134
–
G-value of PCP
455 ꢃ 46
47 ꢃ 5
69 ꢃ 7
60 ꢃ 6
31 ꢃ 3
32 ꢃ 3
8
ꢃ 1

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N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
Table 2
Physicochemical properties of PCP samples.
Reaction system
Polymerization
Color
G (P4 units/100 eV)
6
Phosphorus
content (%)
XRD data
Benzene–propan-2-ol + ionic
liquid ([EOP]NTf2)
In solution
Yellowish orange
56
X-ray amorphous
The shape and morphology of PCP particles were
studied on a Tesla BS 340 scanning electron microscope.
A phosphorus-containing polymer prepared upon the
irradiation of elemental phosphorus in benzene was used
as a reference sample. Fig. 1 shows the micrograph of the
PCP sample.
particles were much smaller than those formed in pure
benzene (11 m). This phenomenon can be due to the fact
that a change from benzene to a more polar solvent is
accompanied by a decrease in the solubility of the polymer
and, finally, the polymer is released at its lower concen-
tration in solution.
m
As found by X-ray diffraction, PCP products formed both
in pure benzene and in benzene–propan-2-ol are X-ray
amorphous.
The similarity of the physicochemical properties
(Table 3) of products formed in the polymerization of
elemental phosphorus in various media suggests
common product formation mechanism.
a
As found by morphological analysis and electron
microscopy, particles with an average size of 0.25
m
m
According to elemental analysis data, the synthesized
PCP mainly consisted of phosphorus (56%); it also
contained carbon (6%), hydrogen (3%), and oxygen
(ꢁ35%). The presence of carbon and hydrogen in the
sample suggests the chemical incorporation of benzene
fragments into the polymer structure of phosphorus
(probably, because of chain termination by organic radicals
were formed in the radiation polymerization process
performed in a polar benzene–propan-2-ol solvent. These
[(ig._1)TD$FIG]
generated by g-radiation).
According to XPS data, the surface composition of the
PCP particles was as follows: E, 68%; O, 22%; and P, 11%.
Note that the carbon content was comparatively high. This
can be due to the sorption of solvent molecules on the
surface of PCP particles (Figs. 2–3).
Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) data for the PCP indicate that
nanosized samples were prepared from solution. They
contained spherical or elliptical particles of size 10–
140 nm; in this case, 45% of the nanopartices were
characterized by a size of 30–50 nm.
As estimated from the empirical formula of the polymer
based on the amount of terminal solvent fragment groups,
the degree of polymerization in solution was n = 5–6
((C4)5–6).
The IR spectra of the PCP exhibited absorption
bands due to P–P stretching vibrations (490–520 cmꢀ1
)
[11,12]. Absorption bands at 1400 and 1010 cmꢀ1
suggest the chemical binding of organic fragments
(benzene) to the phosphorus atoms of the resulting
polymer [13].
Fig. 1. Micrograph of the PCP product prepared by the irradiation of a
solution of white phosphorus in a benzene–propan-2-ol binary solvent
with an ionic liquid added. G = 298 K, Dꢂ = 0.59 Gy/s, D = 24.7 kGy,
[C4]0 = 0.013 ;, and [ionic liquid]0 = 0.16 ;.
Table 3
Physicochemical properties of phosphorus polymer species prepared by the irradiation of a solution of white phosphorus in benzene and the product
prepared in benzene–propan-2-ol with a phosphonium ionic liquid added.
Physicochemical properties
White phosphorus
Sample prepared in
benzene solution
Sample prepared in the
benzene–propan-2-ol–ionic liquid system
Color
White
10ꢀ4 g/l
From light yellow to dark red
Insoluble
From light orange to yellow
Insoluble
Solubility in water
Solubility in organic solvents
Interaction with nonoxidizing acids
Interaction with nitric acid
Inflammability
Soluble
Insoluble
Insoluble
Does not react
Reacts on heating
Spontaneously
flammable in air
Does not react
Does not react
Reacts on heating
Reacts on heating
Spontaneously inflammable;
combustible with the release
of heavy white smoke
Spontaneously inflammable;
combustible with the release of
heavy white smoke

N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
1031
[(ig._2)TD$FIG]
Table 4
Characteristic absorption bands in the IR spectra of PCP samples and their
attribution [12,14,15].
Absorption band
n
(cmꢀ1
)
Intensity
Attribution
1640
Medium
Weak
P(O)–OH, P(O)–H
C–C, C–CPh
C=?
(P)–O–C
C–=, C–E=2
C–?–P
1400
1160
Strong
Strong
Weak
1010
790–810
680–690
490–520
Weak
Medium
C–P
Table 5
XPS data for the PCP.
XPS line
Energy (eV)
Attribution according
to the NIST XPS Database
Fig. 2. Micrographs of product samples prepared by the irradiation of a
solution of white phosphorus in benzene. G = 298 K, Dꢂ = 0.59 Gy/s,
D = 24.7 kGy, and [C4]0 = 0.013 ;.
P 2p3/2
130.3 ꢃ 0.3
P–P
C6H5–P
O=P–C6H5
(O)P–H
P 2p3/2
O 1s
132.8 ꢃ 0.4
532.8 ꢃ 0.2
The occurrence of oxygen in all of the synthesized PCP
samples was due to the partial oxidation of the surface
layers of polymeric phosphorus or the incorporation of
oxygen-containing organic radicals, which initiated the
polymerization process, into the polymer structure. This
manifested itself in the appearance of absorption bands
due to phosphorus-oxygen bonds in the IR spectra
P–P and P–C6H5 bonds and large amounts of oxygen-
containing groups as the constituents of the PCP samples
(Table 5).
The NMR (31P) spectra of PCPs exhibited the presence of
five types of phosphorus nuclei (Figs. 4–5; Table 6):
(Table 4): 1640 cmꢀ1 (H–P=O, HO–P=O), 1160 cmꢀ1
(n
P = O), and 1010 cmꢀ1
(d P–O–C) [11–13]. The bands at
1010 and 1160 cmꢀ1 due to the P–O–C and C = ? bonds,
respectively, exhibited the highest intensities.
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
Singlet at
group [16,17];
Doublet at
ꢄ7 ppm with JPH = 700–720 Hz, which might
be attributed to P–H group;
Triplet at
be attributed to O=P–H or HO–P–H groups;
Wide multiplet (ꢁ1500 Hz) with the centre at ꢁ30 ppm,
which corresponds to P–P polymeric group;
d
ꢁ0 ppm, that might be attributed to P–Ph
Table 5 summarizes the XPS spectra of the PCP samples.
The XPS data support and supplement the results of
instrumental physical studies to indicate the occurrence of
d
d
ꢁ16 ppm with JPH = 550–590 Hz, which might
[(ig._3)TD$FIG]
Wide singlet at
absorption of the P–P group in the white phosphorus
[2,12,17].
d
ꢄꢀ450 (ꢀ460) ppm, attributed to the
The signals in the region 62–81 ppm were attributed to
the side rotation lines of the signals in the region 0–
20 ppm, described above (they are shifted from the main
signals as far as 10 kHz and are characterized with the
same multiplicity and spin-spin coupling constant).
Table 6
Characteristic signals in the NMR (31P) spectra of PCP samples and their
attribution [2,12,17].
Chemical Shift, Multiplicity
ppm
JP-X
Integral,
Attribution
(Hz)
arb. units
ꢀ1.1 ꢃ 0.1
0.4 ꢃ 0.1
4.6 ꢃ 0.1
8.9 ꢃ 0.1
12.0 ꢃ 0.1
15.5 ꢃ 0.1
19.0 ꢃ 0.1
ꢁ24–34
Singlet
Singlet
Doublet
–
0.400
P–CPh
P–H
700 ꢃ 5 0.406
Triplet
585 ꢃ 5 0.110
P–H(O)
Fig. 3. Micrographs of product samples prepared by the irradiation of a
solution of white phosphorus in benzene–propan-2-ol with
a
Wide multiplet
Singlet
0.084
P–C
phosphonium ionic liquid added. G = 298 K, Dꢂ = 0.59 Gy/s, D = 24.7 kGy,
[C4]0 = 0.013 ;, and [ionic liquid]0 = 0.16 ;.
38.6 ꢃ 0.1
P+–Alk

[(ig._4)TD$FIG]
1032
N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
Fig. 4. NMR (31P) spectrum of the PCP sample prepared by the gamma-irradiation of the solution of white phosphorus in the mixed solvent benzene–
propan-2-ol–[EOP]NTf2 (Dꢂ = 0.30 Gy/s, D = 16.7 kGy).
[(ig._5)TD$FIG]
Fig. 5. NMR (31P) spectrum (with the integrals of the signals) of the PCP sample prepared by the gamma-irradiation of the solution of white phosphorus in
the mixed solvent benzene–propan-2-ol–[EOP]NTf2 (Dꢂ = 0.30 Gy/s, D = 16.7 kGy).

[(ig._6)TD$FIG]
N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
1033
Fig. 6. NMR (1H) spectrum (with the integrals of the signals) of the PCP sample prepared by the gamma-irradiation of the solution of white phosphorus in
the mixed solvent benzene–propan-2-ol–[EOP]NTf2 (Dꢂ = 0.30 Gy/s, D = 16.7 kGy).
The 1H NMR spectra of PCPs exhibited the presence of
several types of protons (Fig. 6, Table 7):
5. Reactivity and industrial applicability of PCPs
Polymer phosphorus species can replace white phos-
phorus in organophosphorus synthesis reactions to
compete with commercial red phosphorus. The synthe-
sized samples were tested at A. Favorsky Institute of
Chemistry, Russian Academy of Sciences, Siberian Branch
(Irkutsk).
ꢂ
ꢂ
ꢂ
the singlet (7.7 ppm) attributed to CPh–H;
the signal at 5.1 ppm, that might be attributed to P–H;
the singlet (4.8 ppm), attributed to the proton of the
phosphinic group P(O)–H.
To evaluate the phosphorylating capacity of the
The other signals were difficult to attribute, but one
synthesized PCPs, their interaction with
a-methylstyrene
might suppose them to belong to protons bonded to
phosphorus in different groups, presented in the polymeric
phosphorus structure [18–21] (Table 7).
Thus, we determined the elemental composition of the
synthesized PCPs, supported their polymeric character,
and identified the main functional groups bound to
phosphorus atoms.
in a superbasic medium (the Trofimov-Gusarova reaction,
Fig. 7) was studied in comparison with commercial red
phosphorus.
The reaction occurred on heating (393 K, 3 h) the
r[i(_.gDT)7IF$G] eactants in the KOH–DMSO system with the use of the
Table 7
Characteristic signals in the NMR (1H) spectrum of PCP sample prepared
by the gamma-irradiation of the solution of white phosphorus in the
mixed solvent benzene-propan-2-ol-[(C8H17)(C2H5)3P]+[N(SO2CF3)2]ꢀ
(Dꢂ = 0.30 Gy/s, D = 16.7 kGy) and their attribution [2,12,17].
Chemical shift
(ppm)
Multiplicity
Integral, arb.
units
Attribution
ꢀ0.1 ꢃ 0.1
2.8 ꢃ 0.1
3.4 ꢃ 0.1
4.8 ꢃ 0.1
5.2 ꢃ 0.1
6.6 ꢃ 0.1
7.7 ꢃ 0.1
Singlet
0.325
0.121
(P)–H
(P)–H
Doublet
Singlet
0.071
P(O)–H
P–H
Singlet
Singlet
0.077
0.407
(P)–H
CPh–H
Fig. 7. Reaction scheme of PCP with
a-methylstyrene in a superbasic
medium.

1034
N.P. Tarasova et al. / C. R. Chimie 13 (2010) 1028–1034
Table 8
Acknowledgements
Activity of PCPs in organophosphorus synthesis.
This work was supported by the Russian Foundation for
Sample
Product yield (%)
Basic Research (project no. 09-03-00493, and partly
project no. 08-03-00251).
Commercial red phosphorus
PCP
P4
(GOST [State Standard] 8655–75)
We are grateful to Dr. Katsuhiko Tsunashima (Organic
Chemicals Division, Nippon Chemical Industrial Co., Japan)
for providing us with the phosphonium ionic liquids.
Conversion
83
ꢁ100
100
97
S
(1,2,3)
< 75
95
PCP to form bis(2-phenylpropyl)phosphine oxide 1,
tris(2-phenylpropyl)phosphine oxide 2, and potassium
(2-phenylpropyl)phosphinite 3 (Table 8). The conversion
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&
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