ISSN 1560-0904, Polymer Science, Ser. B, 2006, Vol. 48, Nos. 1–2, pp. 37–45. © Pleiades Publishing, Inc.

, 2006.
Original Russian Text © N.Makhiyanov, D.Kh. Safin, 2006, published in Vysokomolekulyarnye Soedineniya, Ser. B, 2006, Vol. 48, No. 2, pp. 359–369.

METHODS
OF INVESTIGATION

An NMR Study of the Structure and Molecular Characteristics

of Polyether Block Copolymers Based on Propylene Oxide
and Ethylene Oxide
N. Makhiyanov1 and D. Kh. Safin
OAO Nizhnekamskneftekhim,
Nizhnekamsk, 423574 Tatarstan, Russia
Received January 12, 2005;
Revised Manuscript Received October 6, 2005

Abstract—The structure of propylene oxide–ethylene oxide block copolymers prepared with the use of glyc-
erol as an initiator and potassium monoglycerate as a catalyst was studied by NMR spectroscopy. The relative
amounts of oxypropylene and oxyethylene monomer units, the functionality-type distribution, the number-
average molecular mass, and the ratio between primary and secondary terminal hydroxyl groups were deter-
mined. The applicability of 1H and 13C NMR techniques to characterization of these copolymers is discussed.
The obtained NMR data are compared with results obtained by other techniques.
DOI: 10.1134/S1560090406010088

INTRODUCTION where np and ne are the numbers of PO and EO mono-

Random and block copolymers of propylene oxide mer units, respectively. In this case, as suggested by the
(PO) with ethylene oxide (EO) are widely used for the current concepts of the alcohol oxyalkylation mecha-
manufacture of flexible polyurethane foam materials nism [1], anionic oligomerization can yield monofunc-
and oil deemulsifiers. The synthesis of PO–EO block tional polyethers as by-products with the following
copolymers is based on the oxyalkylation reaction of unsaturated end groups:
polyhydric alcohols in the presence of an alkali catalyst
in a nonaqueous medium. Usually, a polyol is oxypro- allyl
pylated at the first step of the process, which is followed
by the addition of monomeric EO units. If glycerol and
ëç2=ëç–ëç2–é–(PO ) n p – 1–(EO ) ne –ç,
potassium monoglycerate are selected as an initiator
and a catalyst, respectively, a trifunctional polyether is
obtained as a result of the two-step oxyalkylation and propenyl
CH2–O–(PO)np–(EO)ne–H
— —

ëç3–ëç=ëç–é–(PO ) n p – 1–(EO ) ne –ç
CH–O–(PO)np–(EO)ne–H
CH2–O–(PO)np–(EO)ne–H, as well as bifunctional polyethers

ç–(EO ) ne –(PO ) n p – 1–é–ëç2–ëç(ëç3)–é–(PO ) n p – 1–(EO ) ne –ç.

The viscosity and hydrophobic–hydrophilic proper-
ties of PO–EO copolymers may vary depending on the
composition, structure, and molecular mass of the
products and the type of initiator (polyol), thus ulti-
mately determining their potential use.
Therefore, it is very important to control their char-
acteristics, such as the mass fraction of the oxyethylene
1 E-mail: nail-nk@rambler.ru
and oxypropylene moieties, the average molecular
mass of the product, the mole fractions of the primary
and secondary hydroxyl end groups, and the mole frac-
tions of molecules with different functionalities (func-
tionality-type distribution, FTD). Although chemical
methods [1, 2], liquid chromatography at the critical
adsorption point [3], and IR spectroscopy are used,
these properties can be determined by 1H [6–15], 13C
[16–20], and 19F NMR [21] techniques. An increase in

37
38 MAKHIYANOV, SAFIN

Table 1. Chemical shifts (as reported in [28]) for 1H and 13C NMR spectra were recorded with Tesla BS-567 (a
NMR lines in deuterated solvents magnetic field strength of 2.35 T), Bruker DRX-500
(11.75 T), and Varian Unity-6000 (14.1 T) spectrome-
Chemical shifts, ppm ters. The samples were solutions with a concentration
Deuterated solvent
1H NMR 13C NMR of 0.5 (1H NMR) or 10 wt % (13C NMR). The 1H NMR
and 13C chemical shifts were measured relative to the
Acetone-d 2.05 29.8 signals of residual protons and carbon-13 nuclei of deu-
terated solvents used (Table 1). The scan repetition
– 206.0
times were 5 and 10 s for proton and carbon NMR spec-
Benzene-d 7.16 128.0 tra, respectively. To eliminate the Overhauser effect in
Chloroform-d 7.27 77.0 quantitative measurements, 13C NMR spectra were
recorded in the inverse gated decoupling mode. The
Toluene-d 2.09 20.4 hydroxyl number (HN) and iodine number (IN) were
7.09, 7.00, 6.98 137.5, 128.9, 128.0, determined according to the conventional procedures
125.2 according to GOST (State Standard) 25261-82 (ASTM
Dimethylsulfoxide-d 2.50 39.5
D 4274-88) and GOST 25240-82 (ASTM D 4671-87),
respectively.

the strength of a static magnetic field and new opportu-
nities for processing NMR spectra have provided
steady progress in NMR studies of these copolymers
[22–27]. The reports that have appeared in the literature
concern only certain individual structural and molecu-
lar characteristics; however, it is quite obvious that the
most important properties of polyether block copoly-
mers are associated with the set of the aforementioned
parameters as a whole.
In this paper, we report the results of 1H and 13C
NMR study of the structure and molecular parameters
of PO–EO polyether block copolymers.
EXPERIMENTAL
The subjects of study were the following commer-
cial PO–EO block copolymers: polyether PP 5043;
Laprols 5003-2-15, 6003-2B-18, and 5003-2B-10 man-
ufactured by the Nizhnekamskneftekhim; and Lupranol
2045 produced by BASF. Their analogs with an average
molecular mass of (5–30) × 102 g/mol prepared in labo-
ratory were also examined. The synthesis of the analogs
was carried out at a reaction-medium temperature of
100–118°C and a pressure of 4.0–6.0 kg/cm2 .
RESULTS AND DISCUSSION
The informative value of the 1H NMR spectra of the
examined samples (Fig. 1, band assignment is given in
Table 2) does not seem to depend on the operating fre-
quency, at least at a first glance. The signals at both
4.0−3.0 and 1.3–0.9 ppm are complex sets of nonsym-
metric lines. This result is due to several reasons:
(1) The broadening of each line by spin–spin cou-
pling of neighboring protons.
(2) Superimposition of the following groups of pro-
ton signals: from protons located inside the sequence
(block) on monomeric units and at the junctions of PO
and EO units; in head-to-tail, head-to-head, and tail-to-
tail dyad combinations of PO units; and in dyadic and
longer combinations of PO units in meso- and racemic
sequences.
(3) The complexity of spin systems formed by pro-
tons in the aforementioned combinations of monomer
units.
Despite that spin–spin interactions of protons in
macromolecular chains appear as if they were broken
by oxygen atoms, the array of factors listed above leads

Table 2. Assignment of 1H NMR spectral regions for propylene oxide–ethylene oxide block copolyethers (acetone-d as a sol-
vent)

Integral intensi-
Chemical shift, ppm Band assignment
ty

5.89, 5.26, 5.11, 3.89 Protons çï, çM, çA, and çD of allyl end groups I1, I2, I3, I4
3.8–3.2 Methine and methylene protons of PO units and methylene protons of EO units I5
Protons of hydroxyl end groups I6
3.1–2.8 Protons of water present in the sample and the deuterated solvent –
2.05 Multiplet of residual protons of acetone-d –
1.4–0.8 Methyl protons of PO units I7

POLYMER SCIENCE Series B Vol. 48 Nos. 1–2 2006

 AN NMR STUDY OF THE STRUCTURE AND MOLECULAR CHARACTERISTICS 39

4 3 2 1
δH, ppm
Fig. 1. 1H NMR spectra of Laprol P-5043 (solvent: acetone-d) at operating frequencies of (1) 100 and (2) 600 MHz.

to considerable complexity of the 1H NMR spectra of
PO–EO polyethers.
According to requirements [28, 29] for the measure-
ment of integral intensity of NMR lines, the set of sig-
nals at 4.0–3.0 ppm is treated as a single entity at any
operating frequency (Fig. 1). In this spectral region, the
signals of EO methylene protons and PO methylene
and methine protons are also displayed. These signals
mask the proton signals of terminal hydroxyl groups.
Thus, it is obvious that the measurement of the integral
intensity of proton signals is impossible for all func-
tional groups except methyl groups (in PO units). These
were the difficulties faced by all investigators in their
attempts to study the structure of polyoxyalkylene by
the NMR technique, beginning from the first studies
[5–7]. It was necessary to introduce a correction for the
amount of polyols used as polymerization initiator into
results calculated from spectral data. In any case, in
order to obtain final information on the composition
and structure of a polymer, it was necessary to know the
average molecular mass of the sample. Various meth-
ods were used to solve this problem. For example, the
derivation of a polyether by trimethylsilylation, end-
capping by isocyanate, etc., with the subsequent deter-
mination of the hydroxyl content per molecule from the
signals of reagent molecules attached to the terminal
OH groups were used [9–11, 13]. The shifting reagents
were also used to make the 1H NMR spectra of poly-
oxyalkylenes more informative [6, 8], but this approach
has not found wide application.
In this study, we managed to obtain 1H NMR spectra
of PO–EO copolyethers in which the proton line of end
hydroxyl groups was distinctly displayed (Fig. 2).
When spectra are recorded under ordinary conditions,
this signal is masked by the intense set of lines of meth-
ylene and methine protons at 4.0–2.8 ppm. It is well
known that the chemical shift of hydroxyl protons
depends on temperature. Increasing temperature to
100–110°C, one can bring the line of interest to the
spectral region between the signals of the right 13C sat-
ellite of the 4.0- to 2.8-ppm set of lines and the
2.09-ppm residual protons of toluene-d. In addition, the
holding of a sample at such a temperature makes it pos-
sible to decrease the amount of moisture contained in
polyether and the deuterated solvent. Measurement of
the integrated intensity of the hydroxyl-proton signal
and its comparison with the area under the signals of all

POLYMER SCIENCE Series B Vol. 48 Nos. 1–2 2006

40 MAKHIYANOV, SAFIN
5 3
δH, ppm
Fig. 2. Portion of the 1H NMR spectrum (100 MHz, toluene-d, 95°C) of low-molecular-mass model compound L-1.
other groups of protons allow the number-average
equivalent mass of the copolyether (number-average
molecular mass per hydroxyl group) to be calculated
(Appendix, Eq. (8)).
The 1H NMR spectra of the samples (Fig. 3) dis-
tinctly displays proton signals of terminal allyl groups.
The following values of spectral parameters were
obtained in an acetone-d solution at an operating fre-
quency of 600 MHz: δÄ = 5.11 ppm, δå = 5.26 ppm,
δï = 5.89 ppm, δD = 3.98 ppm, J(Dï) = 5.1 Hz,
J(AX) = 10.5 Hz, and J(åï) = 17.4 Hz. These data
agree well with the results of measurements at
300 MHz [19]. From the values of integrated intensity
of these lines, it is possible to determine the relative
amount of monofunctional macromolecules, m; how-
ever, it is necessary to know the number-average
molecular mass Mn for this purpose. As will be shown
below, this problem is directly solved by the 13C NMR
technique.
We did not detect proton signals of propenyl end
groups. The absence of these end groups is presumably
due to the procedure used for the removal of the catalyst
from polyethers. Usually, this procedure includes the
addition of water for the hydrolysis of alcoholates and
the subsequent neutralization of the alkali by inorganic
acids, evaporation of water at an elevated (up to 120°C)
temperature, and isolation of the precipitated salts by
pressure filtration. As a result, propenyl groups are
hydrated to yield hydroxyl groups.
Thus, from 1H MNR data, it is possible to calculate
the oxyethylene and oxypropylene mass content per
molecule of PO–EO copolyethers (Appendix, Eq. (1)),
the equivalent mass Me (Eq. (8)), and to determine the
concentration of monofunctional macromolecules.
It is commonplace that spin–spin coupling of 13C
carbons that neighbor in a macromolecular chain is not
POLYMER SCIENCE
1 –1
manifested in carbon NMR spectra because of a low
13C isotopic content. Nonetheless, the 13C NMR spectra
of the samples in question, as in the case of proton
NMR, consist of groups of closely arranged, overlap-
ping lines (Fig. 4, assignment of the basic groups of
lines is given in Table 3). This is a consequence of a
high sensitivity of the chemical shift of 13C NMR sig-
nals toward the diversity of the carbon backbone of
macromolecules. At the same time, a wide range of
chemical shifts of carbon NMR spectroscopy makes it
possible to distinctly distinguish the signals of EO and
PO end units in the array of lines at 80–60 ppm. The
carbon signals of the glycerol “base” are extremely
interesting in our case. According to published data
[20], only one of them, the so-called glycerol carbon at
78–80 ppm, was assigned; the signals of two other
(methylene) carbons have never been mentioned. On
the basis of comparison of the spectra of various sam-
ples, we attribute the lines at 72 ppm to methylene car-
bons of the glycerol base. However, this assignment is
tentative and calls for further investigation.
HA HX
C C
HM CH2 O
HX HM HA
6.0 5.8 5.6 5.4 5.2 5.0
δç, ppm
Fig. 3. Proton NMR spectra (600 MHz, acetone-d) of
allyl end groups of Laprol P-5043 macromolecules.
Series B Vol. 48 Nos. 1–2 2006
 AN NMR STUDY OF THE STRUCTURE AND MOLECULAR CHARACTERISTICS 41
→→
→→→ s – pp eee
–
t – ppp
– → →
→
→
→→
t – –ppp b – pee* (a)
→→→ –
t – ppe
– s – ppp*
– →→
a – ppe*
–
←←→→
s – pppp
–– →
←←→ s – epe*
–
s – ppp
–– a – pee*
–
a – eee*
–
→←
→→
s – epp t – epp*
–
–
→→
t – epp
– →
a – pee*
–
b – eee*
–
→ a – pee*
–
s – eep*
–

80 75 70 65 60
δC, ppm
→
b – ppe*
–
b – eee*
–

→→
→→→
t – epp*
– t – ppp*(meso)
– →→
b – ppe*
–
→
t – eep*
–

68 66 64 62 60
δC, ppm

(b)
→→→
ppp
–
→→
ppe
–

→←
pp
––
→→→
ppp*
–
→→→
ppp*
–

21 20 19 18 17 16 15
δC, ppm
Fig. 4. 13C NMR spectra (125 MHz, benzene-d) of (a) Laprol 5003-2B-10 and (b) methyl end groups of Laprol 5003-2B-
10 macromolecules. The notation used is as proposed in [17]: p and e refer to the PO and EO monomer units, respectively;
the resonating carbons are underlined; the arrows indicate the head-to-head, tail-to-tail, and head-to-tail combinations of
PO units; s and t denote methylene and methine carbons of PO units, respectively; a and b are the left and right carbons
of an EO unit when this unit occurs in a nonsymmetrical sequence of units; and the asterisk marks carbons of end units.

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42 MAKHIYANOV, SAFIN

Table 3. Assignment of 13C NMR spectral regions for propylene oxide–ethylene oxide block copolyethers (acetone-d as a
solvent)

Chemical shift,
Band assignment Integral intensity
ppm
16.5–18.0 Methyl groups of intrachain PO units I8
18.0–19.0 Methyl groups of PO units in head-to-head dyads I9
19.0–20.5 Methyl groups of end PO units I10
61.0–62.5 End EO units I11
65.5–67.5 Methine groups of end PO units I12
68.0–78.0 Intrachain PO and EO units I13
78.5–80.0 Glycerol carbons of trifunctional macromolecules I14
115.5–117.0 (CH2=) carbon atom of allyl end units I15
135.5–137.0 (–CH=) carbon atom of allyl end units I16

There are some data [17] that show a significant dif-
ference between the chemical shifts (0.4–0.5 ppm, or
up to 1.7 ppm for methine carbons of terminal PO units)
of carbons in dyad and triad PO units in meso- and race-
mic sequences. In the spectra obtained in this study
(Fig. 4a), corresponding splitting indeed occurs, except
for the signals of terminal carbons of PO units. It looks
like the chain in dyad and triad combinations of PO
units contain sequences with different tacticities,
whereas the terminal dyads do not. The problem of ste-
reo- and regio-ordering in PO–EO copolymer chains is
subject matter that requires individual consideration;
moreover, information concerning this issue in the lit-
erature is either conflicting or incomplete. For example,
according to Tonelli [30], the difference of chemical
shifts for polyoxypropylene does not exceed
0.2−0.3 ppm. The authors of other studies [16, 18–20,
22–27] did not consider the effect of tacticity in dyad
and triad combinations of monomer units on 13C NMR
spectra.
The portion of the spectrum corresponding to the
resonance of methyl carbon atoms gives a clear picture
of separation of signals according to intrachain and ter-
minal units, as well as units in head-to-head and head-
to-tail dyads and triads (Fig. 4b). The signals of
methine and methylene carbons of PO units are also
responsive to the head-to-head and tail-to-tail dyads;
however, their lines in the spectra are masked by very
intense signals of head-to-tail dyads (region of 77.0–
70.0 ppm in Fig. 4a).
The 13C NMR spectra distinctly display carbon lines
of allyl end units of monofunctional macromolecules
(Table 3). The carbon signals of propenyl end units for
the samples of interest were not detected, a result which
agrees with the proton NMR data.
It is obvious that the following triad combinations of
oxyethyl and oxypropyl monomer units are possible in
the PO–EO copolymer chains: PO–PO–PO, PO–PO–
EO, PO–EO–EO, PO–EO–PO, EO–EO–EO, EO–EO–
PO, EO–PO–PO, and EO–PO–EO. Of course, in the
ideal case when the oxypropylation and oxyethylation
reactions proceed without disturbances, block copoly-
mer macromolecules will have to contain only four
types of triad combination, namely, PO–PO–PO, PO–
PO–EO, PO–EO–EO, and EO–EO–EO. The actual
conditions (especially, for commercial samples) are
such that PO monomer molecules that have not been
consumed at the oxypropylation step and have not been
removed from the system will continue to build in the
chain (by blocks or in single) during oxyethylation.
This conclusion is confirmed for almost every sample
examined. The spectra of the samples clearly show car-
bons in the EO–EO–PO and EO–PO–PO sequences
(Fig. 4a). According to published data [17, 18] on the
carbon chemical shifts in EO–PO–EO and PO–EO–PO
combinations, their signals are masked by grouped
intense and broad carbon lines of the block sequence of
PO and EO units. The potential of 13C NMR spectros-
copy for studying PO–EO block copolymers is not
exhausted by revealing regularity perturbations in mac-
romolecules. From carbon NMR data, it is possible to
calculate the composition of a copolyether (Appendix,
Eq. (2)), the amount of primary and secondary terminal
hydroxyl groups per molecule (Eq. (3)), FTD (mole
fractions m, d, and t of mono-, bi-, and trifunctional
macromolecules, respectively (Eqs.(5)–(7)), and Me
(Eq. (9)).
It was reported [23] that the values of Mn determined
by 13C NMR spectroscopy and from polymerization
and GPC data for the products of anionic copolymer-
ization of PO and EO differ substantially. Obviously,
this difference is due to the specifics of the molecular
structure of the obtained copolymers. In the present
study, we have taken this circumstance into account.
Namely, Me was determined from the parameters of 13C
NMR spectra with correction for the amount of primary

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 AN NMR STUDY OF THE STRUCTURE AND MOLECULAR CHARACTERISTICS 43

Table 4. Composition and molecular parameters of some commercial propylene oxide–ethylene oxide block copolyethers
according to NMR data
Me × 10–3
Specimen OEN OHprim /OHsec FTD (m/d/t) F
13C NMR 1H NMR
Laprol P-5043 0.140 0.73/0.27 0.18/0.34/0.48 2.30 1.7 1.8
Laprol 5003-2-15 0.140 0.70/0.30 0.15/0.35/0.50 2.35 1.7 1.3
Laprol 6003-2B-18 0.175 0.80/0.20 0.22/0.26/0.52 2.30 2.2 2.0
Lupranol 2045 0.135 0.75/0.25 0.20/0.15/0.65 2.45 1.8 1.5
Laprol 5003-2B-10 0.115 0.65/0.35 0.17/0.27/0.56 2.39 1.9 1.4

Table 5. Characterization of some commercial propylene oxide–ethylene oxide block copolyethers by chemical methods
Specimen HN, mg KOH/g Me (at F = 3.0) IN, g I2 /100 g m (at F = 3.0)
Laprol P-5043 35.8 1567 1.64 0.24
Laprol 5003-2-15 35.6 1575 1.48 0.23
Laprol 6003-2B-18 26.3 2133 2.03 0.36
Lupranol 2045 34.9 1607 1.45 0.22
Laprol 5003-2B-10 34.3 1635 1.58 0.24

Table 6. Composition and molecular parameters of some model propylene oxide–ethylene oxide block copolyethers accord-
ing to NMR data
Me × 10–2
Specimen OEN OHprim /OHsec FTD (m/d/t) F
13C NMR 1H NMR
L-1 0.40 0.34/0.66 0.00/0.45/0.55 2.55 3.0 2.5
L-2 0.30 0.42/0.58 0.05/0.10/0.85 2.80 7.0 6.0
L-3 0.28 0.32/0.68 0.03/0.25/0.72 2.69 8.0 6.5
L-4 0.22 0.43/0.57 0.05/0.40/0.55 2.50 8.0 7.0

and secondary hydroxyl groups per molecule (Appen-
dix, Eq. (9)). During calculation of the Mn value of the
product, we also took into account FTD data. This
approach makes it possible to increase considerably the
reliability of determination of Me and Mn .
Considering the data presented in Tables 4 and 6, we
can compare the values of Me obtained by the proton
and carbon NMR techniques. In some cases, these val-
ues differ. Obviously, both proton and carbon NMR
data on Me are somewhat overestimated because of the
presence of macromolecules with nonhydroxyl (e.g.,
allyl end) groups in the products. At the same time, the
supposed presence of water molecules in the samples is
likely to lower noticeably the Me value determined by
1H NMR. According to the given results, the former
factor seems to have a determining effect.
A comparison of Me values obtained from carbon
NMR data (Table 4) and by chemical analysis (Table 5)
shows that they differ for all specimens. This should be
expected. The values of Me presented in Table 5 were
calculated for the maximal functionality, whereas the
NMR-based data were obtained independently from
FTD values. It is easy to see that simple recalculation of
the values of Me with allowance for the FTD data will
lead to good agreement between the results given in
Tables 4 and 5. For the model samples, the values of
functionality are relatively high (Table 6) and, as a con-
sequence, the difference in Me values obtained by
chemical analysis and NMR is not as significant
(Tables 6, 7) as in the case of commercial specimens.
Error in calculations of Me may also be introduced
by incorrect evaluation of the bifunctional molecules
that have been produced via the hydration of mono-
functional molecules with the propenyl end group and
have a functionality of 2 while their molecular mass is
half the mass of the “true” bifunctional molecules. It
should also be taken into account that monofunctional
molecules appear throughout the process and have a
broad molecular-mass distribution (MMD), unlike

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44 MAKHIYANOV, SAFIN
Table 7. Characterization of some model propylene oxide–ethylene oxide block copolyethers by chemical methods
Specimen HN, mg KOH/g Me (at F = 3.0)
L-1 164.0 342
L-2 75.0 748
L-3 74.2 756
L-4 61.7 909
bifunctional molecules, which are formed only at the
beginning of the process. Thus, the molecular mass of
bifunctional molecules of different origin may differ by
more than a factor of 2. As a result, the value of Mn after
calculation may be overestimated.
In turn, during consideration of data on the amount
of primary and secondary hydroxyl groups and FTD, it
is necessary to give attention to measurement accuracy
of integrated line intensities I10, I11, I12, I14, I15 , and I16 .
The accuracy may turn out to be low owing to some
experimental conditions. For example, Carr et al. [20]
reported that the intensity of these lines is very weak
even at a large number of accumulations and that their
relaxation times and nuclear Overhauser enhancements
are abnormal as compared to other signals in the spec-
trum. This becomes especially important in view of the
fact that data on the amount of primary and secondary
hydroxyl groups in the polyethers in question are lack-
ing in the literature and the available data on FTD are
conflicting. For example, Entelis et al. [1] reported the
results of TLC and GPC studies of commercial speci-
mens of glycerol-based polyethers in which the amount
of monofunctional macromolecules did not exceed
3.5 wt % and that of bifunctional macromolecules was
14 wt %. Carr et al. [20] later obtained quite different
results by 13C NMR spectroscopy, namely, the amount
of monofunctional and bifunctional molecules could be
as high as 28 and 15 mol %, respectively.
As regards the FTD data obtained in this study, their
scatter is significant in some lines (Tables 4, 6). For
example, the amount of bifunctional molecules varies
from 15 to 35 mol % for commercial samples and even
widely (from 10 to 45 mol %) for those synthesized
under laboratory conditions. The latter samples are also
characterized by abnormally low values obtained for
the amount of primary hydroxyl groups. This fact can
be explained by incomplete removal of the residual PO
monomer after the oxypropylation step, whose mole-
cules inserted in polyether molecules at the end of
molecular their chain upon the completion of the oxy-
ethylation step.
A comparison of the amounts of monofunctional
macromolecules reveals some discrepancies between
the chemical analysis and the NMR data (Tables 4 vs.
5, and 6 vs. 7, respectively). In most cases, the values of
m calculated from the chemical analysis data (Appen-
dix, Eqs. (11), (12)) are somewhat higher than those
obtained from the NMR data. However, it is easy to see
POLYMER SCIENCE
IN, g I2 /100 g m (at F = 3.0)
0.04 0.002
0.24 0.021
0.29 0.025
0.67 0.067
that substitution of the values of Mn and F obtained by
NMR spectroscopy in Eqs. (11) and (12) used to calcu-
late m leads to good agreement between the results of
chemical analysis and carbon NMR spectroscopy.
The obtained results confirm certain general trends.
Namely, a comparison of the data presented in Tables 4
and 6 shows that the imperfection according to FTD
increases with a growth in chain length, in agreement
with the basic concepts [1] of anionic polymerization of
alkylene oxides.
Thus, it is necessary to take into account the synthe-
sis conditions in the analysis of the molecular structure
of PO–EO polyether block copolymers. In any case,
information on the amount of primary and secondary
hydroxyl groups and FTD data allow values of the
molecular mass obtained by different methods to be
substantially refined.
APPENDIX
The mass content of EO monomer units per mole-
cule of PO–EO copolyethers (the so-called oxyethylene
number, OEN) according to proton NMR data is calcu-
lated by the relationship
OEN = (I5 – I7)/(I5 + 0.76I7), (1)
which gives practically identical results with the
expression for such calculations proposed in the ASTM
D 4875-88 procedure.
According to carbon NMR data, OEN is determined
by the equation
OEN = ( I 11 + I 12 + I 13 – 2 ( I 8 + I 9 + I 10 ) )/ ( I 11
(2)
+ I 12 + I 13 + 0.636 ( I 8 + I 9 + I 10 ) ).
The expression for such calculations given in the
ASTM D 4875-88 procedure does not seem to be cor-
rect. In this standard, the group of lines in the chemical-
shift region of 74–73 ppm is assigned to carbons of PO
units only, although signals due to EO units are also dis-
played in this region (Fig. 4a). As a final result of deter-
mination of OEN, the average value obtained by calcu-
lations with the use of Eqs. (1) and (2) is reported. The
ratio between primary and secondary hydroxyl end
groups is determined as
éçprim /éçsec = I11/I12 (3)
in full agreement with the ASTM D 4273-83 procedure.
Series B Vol. 48 Nos. 1–2 2006
 AN NMR STUDY OF THE STRUCTURE AND MOLECULAR CHARACTERISTICS
Taking m, d, and t as the mole fractions of mono, bi,
and trifunctional molecules, respectively, and F = 3t +
2d + m as the number-average functionality, we can cal-
culate both FTD and functionality values from 13C
NMR data as follows:
m = 2(I15/(I11 + I12 – I14 + I15), (4)
d = (I11 + I12 – 3I14 – I15)/(I11 + I12 – I14 + I15), (5)
t = 2(I14/(I11 + I12 – I14 + I15), (6)
F = 2((I11 + I12)/(I11 + I12 – I14 + I15). (7)
The quantity Me can be determined in two ways. The
first makes use of proton NMR spectroscopy:
Me(1H NMR) = 58I7/(3I6(1 – OEN)). (8)
When Me is calculated from carbon NMR data, infor-
mation on the amount of primary and secondary
hydroxyl end groups is taken into account:
Me (13C NMR) = 58(I8 + I9 + I10)/((I10 + I11)(1 – OEN))(9)
In quantitation by NMR, the following relationships
were maintained:
I1 = I2 = I3 = 0.5I4, I10 = I12, and I15 = I16 .
From chemical analysis data (by HN), it is possible
to determine the number-average molecular mass:
Mn = 56100 × F/HN. (10)
It is easy to show that values of m can be obtained
from chemical analysis data by two methods. The first
makes use of the iodine number as a characteristic of
the unsaturated-bond content:
m = (IN · Mn)/(IN · Mn + 25400). (11)
The second method of calculation of m requires both
the iodine number and the hydroxyl number to be
known:
m = (56 × F · IN)/(25.4 × HN + 56 × IN · (F – 1)).(12)
The ultimate value of the index m is determined by aver-
aging the results of calculation by Eqs. (11) and (12).
To obtain and interpret quantitative data by both
chemical methods and NMR spectroscopy, we used the
relationship Mn = FMe .
ACKNOWLEDGMENTS
The authors are greatly indebted to A.S. Kha-
chaturov (Lebedev Research Institute of Synthetic
Rubber), A.Z. Gurevich (Russian representative for
Varian Inc.), and A.Sh. Mukhtarov for assistance in
recording NMR spectra and helpful discussion of the
results of this study.
POLYMER SCIENCE Series B Vol. 48 Nos. 1–2
45
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