Volatility of some aromatic nitrosubstituted plasticizers for polymers

Article abstract of DOI:10.1134/S1070363217090456

Nine derivatives of nitrophthalic acids and nitrophenols were synthesized as potential plasticizers for polymers and structurally characterized by ¹H NMR and elemental analysis. The time dependences of the weight loss for the nitro derivatives

Full text of DOI:10.1134/S1070363217090456

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 9, pp. 2188–2194. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.E. Golubev, I.V. Novikov, S.A. Kuvshinova, V.A. Burmistrov, O.I. Koifman, 2015, published in Rossiiskii Khimicheskii Zhurnal,
2015, Vol. 59, No. 4, pp. 58–65.
Volatility of Some Aromatic Nitrosubstituted Plasticizers
for Polymers
A. E. Golubeva*, I. V. Novikovb, S. A. Kuvshinovab**,
V. A. Burmistrovb***, and O. I. Koifmanb,c****
a Research Institute of Polymer Materials, ul. Chistopol’skaya 16, Perm, 614101 Russia
e-mail: *niipm@perm.ru; **sofya.kuv@yandex.ru; ***burmistrov@isuct.ru; ****oik@isuct.ru
b Ivanovo State University of Chemistry and Technology, Sheremetevskii pr. 7, Ivanovo, 153000 Russia
c Krestov Institute of Solution Chemistry, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
Received March 1, 2015
Abstract—Nine derivatives of nitrophthalic acids and nitrophenols were synthesized as potential plasticizers
1
for polymers and structurally characterized by H NMR and elemental analysis. The time dependences of the
weight loss for the nitro derivatives synthesized and for commercial plasticizers (dibutyl phthalate and dioctyl
phthalate) were obtained by gravimetric method at 100ºC, and their volatilities and dipole moments were
calculated. The resultant nitroplasticizers are considerably less volatile than dibutyl phthalate. Low volatility is
associated not so much with high molecular weight as with high polarity. The nitroplasticizers are well compatible
with cellulose esters and exhibit low rates of migration from polymer films.
Keywords: volatility, nitrosubstituted plasticizers, dibutyl phthalate, cellulose esters, dipole moments, polarity,
polymer
DOI: 10.1134/S1070363217090456
INTRODUCTION
good plasticizing efficiency, and high photostability
and are compatible with many polymers. Even when
introduced in relatively small amounts into polymers,
low-molecular-weight derivatives of phthalic acid
solvate the polar groups of the latter, thereby weaken-
ing their interactions [9]. In [10], this process was
effectively promoted via introduction of polar
moieties, e.g., nitro groups, into the structure of
potential plasticizers. High polarity of dialkoxyethyl-4-
nitrophthalates was shown [10] to enhance their thermo-
dynamic affinity to nitrocellulose, thereby eventually
improving the compatibility and effectiveness of the
plasticizing action.
Hard-chain polymers, e.g., polyvinylchloride, cellulose
diacetate, nitrocellulose, etc., exhibit increased
brittleness, which renders practically impossible the
use of products thereof under low temperature condi-
tions. The low-temperature properties of polymers and
products thereof can be improved, and their processing
temperature can be reduced, through the use of
plasticizers, special agents increasing the mobility of
the structural elements of polymers [1–4]. This
increases the deformability of the plasticized polymer,
broadens the range of their service temperatures
toward lower temperatures, reduces the brittleness
temperature, and improves the processabilty of poly-
mers in melt [3, 4].
Further properties of chemical additives that make
them suitable as plasticizers are high boiling point
(>250°C) and flash point (>160°C), low flammability,
chemical resistance to various agents (fuels, oils, etc.),
thermal and photochemical stability, non-toxicity, and
inexpensiveness [11]. Virtually the main recognized
characteristic of potential plasticizers is low volatility
at the polymer processing and service temperatures.
Currently, there exists a fairly wide range of
commercial plasticizers [2, 5, 6], among which esters
of phthalic acid and aliphatic alcohols (phthalates) are
recognized as the major group [7, 8]. Being
inexpensive, phthalates exhibit high heat resistance,
2188

VOLATILITY OF SOME AROMATIC NITROSUBSTITUTED PLASTICIZERS FOR POLYMERS
2189
1
Specifically high volatility of dibutyl phthalate (DBP),
despite all the advantages, poses certain constraints on
its use as plasticizer. However, data on the volatility of
the substances making part of polymer compositions
are scarce and, moreover, scattered and often random.
For example, volatilities of new plasticizers for
polyvinylchloride, interaction products of fatty acids
and 1,4-butanediol, were reported in [12]. The volatility
of phenolic and amine stabilizers of polymers was
estimated in [13].
2
3
4
6
5
In view of the above-said, we estimated herein the
volatility of a number of potential plasticizers of
polymer compositions, derivatives of nitrophthalic
acids and nitrophenols, and determined how this
characteristic is affected by the chemical structure of
the compounds tested.
Fig. 1. Schematic diagram of the setup for volatility
determination: (1) torsion balance (weighing range 500 mg,
division value 1 mg), (2) metallic thread, 0.05 mm in
diameter, (3) glass tube, 30 mm in diameter, (4) branch for
gas supply, (5) glass cup, 14.5 mm in diameter and 5 mm
in height, for the weighed portion of the plasticizer, and
(6) thermostat.
EXPERIMENTAL
In our experiments, 3- and 4-nitrophthalic acids, 2,4-
dinitrophenol, n-butyl, n-propyl, and ethyl alcohols,
propionyl chloride, amyl bromide, bromohexadecane,
potash, dimethylformamide, triethylamine, and
chloroform (all purchased from Sigma-Aldrich) were
used without further purification. 4-Nitrophenol
(“Vekton”) was recrystallized from water, and 2,5-
dinitrophenol (“Vekton”), from a 2 : 3 ethanol-water
mixture. Plasticizers dioctyl phthalate (DOP) and DBP
(OOO Roshal’ Plasticizers Plant, Moscow oblast) were
used without further purification.
inside the tube at the sample level was checked by
using control mercury thermometers. The thermostat
was preheated to the preset temperature, and the
weighing operation was performed immediately after
the cup with the weighed portion of the sample sank.
As a result of the measurements, the time dependence
of the weight loss was plotted.
The 1H NMR spectra were recorded, and the
chemical shifts were measured on a Bruker-Avance 3
high-resolution spectrometer (operating frequency
500 MHz); CDCl3 was used for proton stabilization.
Chemical shifts were measured relative to tetra-
methylsilane in ppm (δ-scale) accurately to within
0.01 ppm.
Di-n-butyl ester of 4-nitrophthalic acid (1).
0.1 mol of 4-nitrophthalic acid, 0.5 mol of butanol-1,
and a catalytic amount (1.5% of the weight of 4-
nitrophthalic acid) of concentrated sulfuric acid were
placed in a round-bottomed flask equipped with a
Dean-Stark trap, a reflux condenser, and a stirrer. The
reaction mixture was heated with stirring to boiling of
the reaction mixture and separation of a part of the
alcohol and the reaction water in the trap. Upon
heating for 15 h the excess alcohol was distilled off.
To remove acidic impurities (residues of sulfuric acid,
alkyl sulfuric acid, 4-nitrophthalic acid, and monoalkyl
phthalate) the product was poured into water and
alkalified with 20% soda solution to a slightly alkaline
reaction. Next, the product was extracted with chloro-
form, the organic layer was washed several times with
water in a separatory funnel, separated, dried with
anhydrous sodium sulfate, and filtered. Silica gel was
poured into the product solution in chloroform, left for
1 h, and filtered. Chloroform was distilled off. Yield
Elemental analysis data were obtained with a Flash
EA 1112 Series CHNS-O Analyzer.
The volatility of the commercial and synthesized
plasticizers was determined from the loss in weight of
the substance over time in the setup shown schema-
tically Fig. 1.
A glass cup with the weighed portion of the plas-
ticizer was suspended by a metallic thread to the lever
of the torsion balance. The thermostat temperature was
adjusted with a contact thermometer accurately to
within 0.5°C. The correspondence between the tempera-
tures of the coolant in the thermostat and of the gas
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 9 2017

2190
GOLUBEV et al.
96%, light yellow oily liquid. Found, %: C 59.03; H
6.37; N 4.17. C16H21NO6. Calculated, %: C 59.43; H
6.55; N 4.33. H NMR spectrum, δ, ppm: 8.38 s; 8.20
d; 7.68 d (3H, Ar); 4.19 t (4H, OCH2); 1.59 m (4H,
CH2); 1.30 m (4H, CH2); 0.81 t (6H, CH3).
%: C 44.85; H 3.22; N 11.54. C9H8N2O6. Calculated,
%: C 45.01; H 3.36; N 11.66.
1
2,5-Dinitrophenyl ester of propionic acid (6) was
prepared by a procedure similar to that used for ester 7.
Yield 88%, yellow platelet crystals, mp 84°C. Found,
%: C 44.87; H 3.21; N 11.53. C9H8N2O6. Calculated,
%: C, 45.01; H 3.36; N 11.66.
Di-n-propyl and diethyl esters of 4-nitrophthalic
acid, as well as di-n-butyl and di-n-propyl esters of
3-nitrophthalic acid, were obtained under similar
conditions at the same ratio of reactants.
Pentyloxy-2,5-dinitrobenzene (9). The reaction
mixture consisting of 0.11 mol of 2,5-dinitrophenol,
0.5 mol of potash, and 0.1 mol of amyl bromide in
150 mL of dimethylformamide was refluxed under
vigorous stirring for 10 h, then cooled, poured into ice-
cold water, and left for 3–5 h. The product was
extracted with ether, the organic layer was washed 5–
7 times with water, separated in the separatory funnel,
and dried with anhydrous sodium sulfate, whereupon
the solvent was distilled off. For purification, the
product was recrystallized from ethanol and subjected
to column chromatography over silica gel (eluent
chloroform). Yield 87%, reddish yellow shiny crystals,
mp 36°C. Found, %: C 51.90; H 5.48; N 10.96.
C11H14N2O5. Calculated, %: C 51.97; H 5.55; N 11.02.
1H NMR spectrum, δ, ppm: 7.90 m (3H, Ar); 4.21 t
(2H, OCH2); 1.88 m (2H, CH2); 1.47 m (2H, CH2);
1.40 m (2H, CH2); 0.93 t (3H, CH3).
Di-n-propyl ester of 4-nitrophthalic acid (2).
Yield 97%, light yellow oily liquid. Found, %: C
56.57; H 5.63; N 4.53. C14H17NO6. Calculated, %: C
1
59.43; H 6.55; N 4.33. H NMR spectrum, δ, ppm:
8.55 s; 8.33 d; 7.82 d (3H, Ar); 4.27 t (4H, OCH2);
1.75 m (4H, CH2); 0.96 t (6H, CH3).
Diethyl ester of 4-nitrophthalic acid (3). Yield
97%, light yellow solid, mp 25°C. Found, %: C 53.60;
H 4.78; N 5.16. C12H13NO6. Calculated, %: C 53.93; H
4.90; N 5.24. 1H NMR spectrum, δ, ppm: 8.51 s; 8.30 d;
7.77 d (3H, Ar); 4.34 m (4H, OCH2); 1.34 t (6H, CH3).
Di-n-butyl ester of 3-nitrophthalic acid (4). Yield
95%, colorless oily liquid. Found, %: C 59.31; H 6.42;
N 4.09. C16H21NO6. Calculated, %: C 59.43; H 6.55; N
4.33. 1H NMR spectrum, δ, ppm: 8. 00 t (1H, Ar); 7.97
t (1H, Ar); 7.26 t (1H, Ar); 4.25 t (3H, OCH2); 4.21 t
(3H, OCH2); 1.55 m (8H, CH2); 0.91 t (6H, CH3).
Hexadecanoxy-4-nitrobenzene (8) was prepared
under conditions and reactant ratios identical to those
used for 9. Yield 73%, light yellow crystals, mp 62°C.
Found, %: C 72.60; H 10.19; N 3.78. C22H37NO3.
Calculated: C 72.69; H 10.26; N 3.85. 1H NMR
spectrum, δ, ppm: 8.21 d (2H, NO2-Ar); 6.96 d (2H,
Ar-OCH2); 4.06 t (2H, OCH2); 1.83 m (2H, CH2); 1.48
m (2H, CH2); 1.27 m (24H, CH2); 0.89 t (3H, CH3).
Di-n-propyl ester of 3-nitrophthalic acid (5).
Yield 96%, colorless oily liquid. Found, %: C 56.77; H
5.69; N 4.60. C14H17NO6. Calculated, %: C 59.43; H
1
6.55; N 4.33. H NMR spectrum, δ, ppm: 8.28 d (1H,
Ar); 7.68 m (2H, Ar); 4.36 t (2H, OCH2); 4.28 t (2H,
OCH2); 1.77 m (4H, CH2); 0.99 t (6H, CH3).
2,4-Dinitrophenyl ester of propionic acid (7).
Into a three-necked round-bottomed flask equipped
with a mechanical stirrer, a reflux condenser, and a
dropping funnel, 0.1 mol of 2,4-dinitrophenol, 70 mL
of chloroform, and 15 mL of triethylamine were
placed. Into the solution thus obtained, 0.1 mol of
propionic acid chloride was added dropwise with
vigorous stirring for 30 min. The resulting mixture was
stirred for 2 h at room temperature and then refluxed
for 12 h. Next the solvent was distilled off, whereupon
the residue was transferred into ice-cold water and left
for 2 h. The product was filtered off, washed with
water, and dried. For purification the product was
recrystallized from ethanol and subjected to column
chromatography over silica gel (eluent chloroform).
Yield 92%, yellow platelet crystals, mp 72°C. Found,
RESULTS AND DISCUSSION
Di-n-butyl, di-n-propyl, and diethyl esters of 4-
nitrophthalic acid (1, 2, and 3, respectively), di-n-butyl
and di-n-propyl esters of 3-nitrophthalic acid (4 and 5),
2,5- and 2,4-dinitrophenyl esters of propionic acid (6
and 7, respectively), hexadecanoxy-4-nitrobenzene (8),
and pentyloxy-2,5-dinitrobenzene (9) (see Scheme 1)
were synthesized as research subjects, potential
plasticizers.
Nitrophthalates 1–5 were prepared by esterification
of 4- or 3-nitrophthalic acids with appropriate alcohols
in the presence of catalytic amounts of concentrated
sulfuric acid. To this end, the reaction mixture was
refluxed for 8–12 h using a 5-fold excess of alcohol.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 9 2017

VOLATILITY OF SOME AROMATIC NITROSUBSTITUTED PLASTICIZERS FOR POLYMERS
2191
Scheme 1.
O
C
O
C
ROH, H2SO4
OH
OH
OR
OR
O2N
C
O
O2N
C
O
R = C4H9 (1); C3H7 (2); C2H5 (3).
O
C
O
C
ROH, H2SO4
OR
OR
OH
OH
C
C
O
NO2
NO2
O
R = C4H9 (4); C3H7 (5).
NO2
HO
NO2
O2N
H3CH2CCOO
H3CH2CCOO
NO2
O2N
O
6
HO
CH3CH2C
NO2
Cl
O2N
O2N
7
C13H33Cl
C16H33O
NO2
NO2
NO2
HO
K2CO3, DMF
8
NO2
C5H11Br
HO
O2N
C5H11O
O2N
K2CO3, DMF
9
Prolonged heating is required for the esterification of 3
-nitrophthalic acid due to steric limitations in the
synthesis of di-n-butyl phthalates as well.
hydrogen chloride acceptor (esters 6 and 7). Nitro-
phenols were alkylated with haloalkyls in dimethyl-
formamide in the presence of potash (compounds 8
and 9).
Dinitrophenols were acylated with propionic acid
chloride by refluxing equimolar amounts of the reac-
tants in chloroform in the presence of triethylamine as
The structure of the compounds synthesized was
confirmed by elemental analysis and 1H NMR spectro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 9 2017

2192
Δm, mg
GOLUBEV et al.
14.00
1
12.00
2
4
Δm, mg
3
5
10.00
1
6
12.00
2
3
8.00
6.00
4
8.00
4.00
4.00
2.00
0.00
5
0.00
0
20
40
60
80
100 120 140
0
20 40 60 80 100 120 140 160 180
τ, min
τ, min
Fig. 3. Time dependences of the weight loss for nitro-
phenol derivatives: (1) DBP, (2) 6, (3) 7, (4) 9, and (5) 8.
Fig. 2. Time dependences of the weight loss for phthalates:
(1) DBP, (2) 1, (3) 2, (4) 5, (5) 4, and (6) 3.
scopy. For the elemental analysis data and for the
yields and melting points of the end products, as well
as for the assignment of the signals in the spectra, see
Experimental.
consumer qualities of films, fibers, membranes, etc. In
this connection, we studied the volatility of the
potential plasticizers synthesized by the gravimetric
method at 100°C. The choice of this temperature was
dictated by the fact that nitrocellulose etrols (celluloid)
are processed at temperatures above their softening
point of 80–90°C. For comparison, under identical
conditions we determined the volatility of DBP and
DOP as the most widely used plasticizers.
Most polymers are processed in melt at elevated
temperatures, which makes volatility (evaporation rate)
one of the main characteristics of plasticizers. The
volatility of plasticizing additives is essential in
evaluating their effectiveness. For example, during
heat treatment of polymer compositions or during
service of products thereof, some part of plasticizers
can migrate from the polymer without being involved
in the plasticization, thereby deteriorating the
The time dependences of the weight loss (Figs. 2
and 3) for all the compounds tested are approximated
by straight lines due to a constant evaporation rate
observed at unchanged temperature and evaporation
Table 1. Volatility and dipole moments of the plasticizers
Molecular weight
Weight loss
after 1 h, g/h
Volatility,
Volatility relative to
DBP
Dipole moment D, D
Plasticizer
M, g/mol
mg cm–2 h–1
(AM1)
DOP
390.56
278.40
323.34
295.29
267.24
323.34
295.29
240.17
240.17
363.54
254.24
4.15
6.60
5.90
5.10
3.35
3.85
5.30
5.33
4.61
2.10
3.45
3.24
3.98
3.63
3.24
2.00
2.26
3.08
3.11
2.77
1.35
2.15
0.81
1.00
0.91
0.81
0.50
0.57
0.77
0.78
0.70
0.34
0.54
2.2
2.7
5.5
5.7
5.2
6.1
6.3
1.8
4.9
6.7
2.4
DBP
1
2
3
4
5
6
7
8
9
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 9 2017

VOLATILITY OF SOME AROMATIC NITROSUBSTITUTED PLASTICIZERS FOR POLYMERS
Table 2. Volatility of the film samples
Polymer
Volatility, mg cm–2 h–1
2193
Plasticizer
Weight loss after 1 h, mg/h
CDA
CDA
CDA
NC
DBP
0.0042
0.0035
0.0017
0.0025
0.0018
0.95
0.76
0.40
0.56
0.46
1
9
DBP
NC
1
area. The same induction period for all samples (~10
min) was observed due to arising of nonstationary
evaporation during heating of the plasticizers to the
experimental temperature. We associate the occurrence
of an induction period with heat transfer exclusively,
and this is confirmed by its independence on the nature
of the compounds studied.
effect of alkyl substituents with their lengthening,
which weakens the dipole-dipole interactions, thereby
decreasing the cohesion energy. This assumption is
indirectly confirmed by the fact that 4-nitrophthalic
acid diethyl ester 3, despite its smallest size among the
nitrophthalates, is a solid at room temperature. As
known, the crystal lattice energy is maximal at the
closest rapprochement of interacting molecules, which
is least hindered by short substituents in diester 3.
Most likely, the same factors are responsible for low
volatility of dinitrophenol derivatives 6, 7, and 9,
which have the lowest molecular weights and dipole
moments among the substances of interest, but which
are crystalline products.
Table 1 lists the experimental volatilities of the
plasticizers and their dipole moments calculated by the
AM1 method. These data do not reveal unambiguous
trends in the influence exerted on these characteristics
by the molecular structure of the compounds of
interest. Obviously, the volatility of a substance is
directly related to its cohesion energy which, in turn, is
determined by various contributions, from both Van
der Waals forces and specific forces, to the
intermolecular interaction energy. The intensity of the
dispersion interactions is mainly determined by the
size and polarizability of the molecules, while the
dipole-dipole contacts are directly associated with the
molecular dipole moments. Moreover, each of the
interaction types is directly affected by the molecular
geometry: symmetry, complementarity, and conforma-
tional transition capability. Hence, a lower volatility of
DOP as compared to DBP is attributable to a
substantially larger weight of the molecule of the
former and to enhanced dispersion interactions. In the
case of compounds 1, 2, 4, 5, and 8, the volatility may
be suppressed upon introduction of a nitro group into
the molecule because of increases in both the weight
and polarity.
Considering significantly lower volatilities of the
alkoxynitrophthalates and substituted nitrophenols
synthesized as compared to DBP it was reasonable to
expect their higher thermodynamic affinity with
polymers and, consequently, lower migration rates
from polymers at high temperatures. To check the
assumption, we plotted the time dependences of the
Δm, mg
1
8.00
2
6.00
4
3
5
4.00
2.00
0.00
Notably, progressive lengthening of aliphatic substi-
tuents caused the volatility of the 4-nitrophthalate
diesters to markedly increase as 3 < 2 < 1 (Table 1,
Fig. 2, curves 1–3 and 6). This experimental fact
cannot be explained by the effect of the dipole moment
exclusively. In our opinion, it can be reasonably
interpreted as due to enhancement of the loosening
0
20 40 60 80 100 120 140 160 180
τ, min
Fig. 4. Time dependences of the weight loss of the CDA-
and NC-based film samples: (1) CDA + DBP, (2) CDA + 1,
(3) NC + DBP, (4) NC + 1, (5) CDA + 9.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 9 2017

2194
GOLUBEV et al.
weight loss of the film samples based on cellulose
diacetate (CDA) and cellulose nitrate (NC, nitrogen
content 11%) (Fig. 4). The films were prepared by dry
spinning from 10% solutions in cyclohexanone. As
plasticizers for testing we chose di-n-butyl ester of
4-nitrophthalic acid (1) as a structural analog of DBP
and pentyloxy-2,5-dinitrobenzene (9) as the least
volatile among the substances synthesized. The results
were compared with those for the films plasticized
with DBP. The content of the plasticizers in all the
samples was identical, 23 wt%. Prior to the experiment
the films were dried with subsequent evacuation at a
residual pressure of 200 Pa at 313.15±1 K to constant
weight. The film thickness measured with an ISV-1
thickness gauge accurately to within 0.5 μm was 37–
41 μm.
ACKNOWLEDGMENTS
This study was carried out within the framework of
the State task of the Ministry of Education and Science
of the Russian Federation.
REFERENCES
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dependences of the weight loss of the film samples are
represented by straight lines and exhibit an induction
period identical for all the films as associated with the
heat transfer during heating to the experimental
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1 and dinitro
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with DBP. In our opinion, this is due to the ability of
the nitroplasticizers to interact effectively with
polymer macromolecules via solvating their polar
groups and to stay longer in the polymer, thereby
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CONCLUSIONS
10. Bogdanov, A.P., K voprosu plastifikatsii nitratov tsellyu-
lozy alkoksinitroftalatami (On the Issue of Plasticization
of Cellulose Nitrates with Alkoxynitrophthalates),
Bogdanov, A.P. and Geisman, I.I., Eds., Available from
ONIITEKhIM, 1978, Kazan, no. 1449/78.
Thus, nine new derivatives of nitrophthalic acids
and nitrophenols were synthesized and structurally
identified. Time dependences of the weight loss of the
potential plasticizers were obtained by gravimetric
method at 100°C, and their volatilities and dipole
moments were calculated. By contrast to DBP, all the
substances synthesized were characterized by high
polarity and low volatility. This allows them to be well-
compatible with polymers, in particular with cellulose
nitrates and acetates, and to be able to effectively
reduce their glass transition temperature and to
decrease the migration rate from polymer films, thereby
preserving their good physicomechanical properties.
11. Gotlib, E.M., Plastifikatsiya polyarnykh kauchukov,
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