European Polymer Journal 37 (2001) 705±710

Spontaneous copolymerization of acrylic acid with

4-vinylpyridine and microscopic acid dissociation of the
alternating copolymer
Seizo Masuda a,*, Keiji Minagawa a, Masanori Tsuda a, Masami Tanaka b
a
Faculty of Engineering, Department of Chemical Science and Technology, The University of Tokushima, Minamijosanjima-cho,
Tokushima 770-8506, Japan
b
Faculty of Pharmaceutical Science, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan
Received 1 February 2000; received in revised form 30 May 2000; accepted 20 July 2000

Abstract
A large amount of heat was generated by mixing concentrated acrylic acid and concentrated 4-vinylpyridine, which
led to carbonized products. When they were mixed within the limited concentration range, however, the polymerization
took place spontaneously, and gave the alternating copolymer a relatively low molecular weight. The copolymerization
was accelerated by a cationic catalyst, and inhibited by butylamine although it was not accelerated by a radical initiator
and was not inhibited by a radical inhibitor. These ®ndings suggest that the spontaneous copolymerization proceeds via
cationic mechanism. However, copolymerization is accelerated by water, which is a typical inhibitor of ionic poly-
merization.
Macroscopic and microscopic acid dissociation constants of the alternating copolymer were determined by pH-
titration method. The relative concentrations of respective microscopic forms were calculated using the relation between
micro-constants and hydrogen ion concentration. The fraction of the protonated form, which exists exclusively in the
lower pH range, decreases with increasing pH value, and fully vanishes at pH  6, while the deprotonated form begins
to appear from about pH ˆ 9. The zwitterionic and neutral molecule forms coexist over a wide range of pH, and the
latter form is predominant regardless of the pH value. Macro- and micro-constants were also measured for the system
of monomer mixtures, and homopolymer mixtures as well. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Acrylic acid; 4-Vinylpyridine; Spontaneous copolymerization; Alternating copolymer; Microscopic acid dissociation
constants; Distribution of microscopic forms

1. Introduction teristics of amphoteric compounds. For many compounds

In general, amino acids exist as the protonated form
in acidic region, and deprotonated form in basic region.
And there are coexistence of zwitterionic and neutral
molecule forms in neutral region. Such a behavior of
microscopic forms depending pH is one of the charac-
*
Corresponding author. Tel.: +81-88-656-7407; fax: +81-88-
655-7025.
E-mail address: masuda@chem.tokushima-u.ac.jp (S. Ma-
suda).
(e.g., amino acids [1,2], oligopeptides [3,4], pyridine de-
rivatives [5,6], and drugs [7,8]), macroscopic and mi-
croscopic acid dissociation constants have been
determined from the point of view of relationship be-
tween pharmacological and biological activities and the
degree of ionization. However, there is no report on
the microscopic acid dissociation of synthetic polymers,
despite many works on macroscopic acid dissociation of
polyelectrolites [9±12].
Poly(2-aminoacrylic acid) is a typical example of a
acid±base equilibria of synthetic polymers having an
amino and carboxyl groups. Poly(2-aminoacrylic acid) is

0014-3057/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 4 - 3 0 5 7 ( 0 0 ) 0 0 1 5 9 - 2
706 S. Masuda et al. / European Polymer Journal 37 (2001) 705±710
prepared by hydrolysis of poly(2-acetylaminoacrylic
acid) [13,14]. Though poly(2-acetylaminoacrylic acid) is
easily soluble in water [15], poly(2-aminoacrylic acid) is
precipitated during hydrolysis because of insolubility in
water. Therefore, the dissociation constant of poly(2-
aminoacrylic acid) in aqueous solution is dicult to
estimate.
The present paper is concerned with the preparation
of the alternating copolymer of acrylic acid (AA) with 4-
vinylpyridine (4VP), and determination of microscopic
acid dissociation constants of the copolymer. The AA±
4VP copolymer is an amphoteric compound, in which a
proton of carboxyl group can migrate to nitrogen atom
of the pyridine ring (interconversion of neutral molecule
form to zwitterionic form).
Mixing of concentrated AA and concentrated 4VP
led to carbonized products with the generation of a large
amount of heat. When they were mixed within the lim-
ited concentration range, however, the copolymerization
took place spontaneously without generation of heat
and gave an alternating copolymer with a low molecular
weight.
Several papers on spontaneous polymerization of
amphoteric vinyl monomers (methacrylic derivatives of
sodium phosphates [16,17], and quarternary ammonium
halides [18] with a long alkyl chain, and vinyl pyridinium
derivatives [19±21]) were published. Spontaneous poly-
merization of amphoteric vinyl monomers is known to
take place radically at the concentration above critical
micellar concentration. However, spontaneous copoly-
merization of AA, and 4VP appears to proceed via non-
radical mechanism because it is not accelerated by a
radical initiator and is not inhibited by a radical inhib-
itor.
2. Experimental
2.1. Materials
Boron tri¯uoride ethyl etherate and butyllithium
were of special grade and used without further puri-
®cation. Monomers (AA, 4VP, and methyl acrylate
(MA)), additives (2,20 -azobisisobutyronitrile (AIBN), p-
benzoquinone (BQ), acetic acid, and butylamine), and
solvents were commercially available and puri®ed by
standard methods prior to use.
2.2. Copolymerization procedure
Copolymerization of AA with 4VP in ethanol was
carried out at a given temperature in sealed tubes
without any catalyst. Methyl acrylate (MA) and 4VP
were copolymerized at 60°C with AIBN as the initiator.
The 1:1 copolymer of MA and 4VP is required as a
reference sample for the determination of micro-
constants for AA±4VP copolymer.
Monomers, solvent, and additive (if necessary) were
placed into the tube and degassed by successive freeze±
pump±thaw cycles. After a ®xed time, the contents were
brought together with a large amount of ether so that
copolymer precipitated. The copolymer was ®ltered o€,
dried under reduced pressure, and weighed. The AA±
4VP and MA±4VP copolymers were puri®ed by dialy-
zation and lyophilization. Copolymer composition was
determined by 1 H-NMR spectroscopy.
2.3. pH-titration
The copolymer was dissolved in the mixed solvent
(1:1 by volume) of ethanol and water, the concentration
being 2:5  10ÿ3 mol lÿ1 . The calculated amount of nitric
acid equivalent to the content of vinylpyridine units in
the copolymer was added to the solution, followed by
potassium nitrate to keep the ion strength (l ˆ 0:1). The
solution was then titrated with 0.02 N potassium hy-
droxide. Monomer mixture and homopolymer mixture
were also titrated. pH-measurements were made at 25°C
with a TOA HS-60S pH-meter and equipped with an
automatic titrator.
2.4. Other measurements
Number average molecular weight was determined
by the GPC method, relative to polyethylene glycol. 1 H-
NMR spectra were obtained with a JEOL GX-400
spectrometer, using deuterated water and tetramethyl-
silane (TMS) as the solvent and standard, respectively.
UV spectra were measured on a Shimadzu UV-3000
spectrometer, using ethanol as the solvent.
3. Results and discussion
3.1. Spontaneous copolymerization of AA with 4VP
The spontaneous copolymerization of AA with
4VP was carried out at a ®xed ratio of monomers in
feed …‰AAŠ=‰4VPŠ  1†. As indicated in Fig. 1, the rate
(conversion per unit time) increases with an increasing
concentration of total monomers. However, no poly-
merization takes place in the concentration up to 1
mol lÿ1 . Such a dependence of the rate on monomer
concentration was observed in the spontaneous homo-
polymerization of vinylpyridium salt [22]. The 1 H-NMR
spectrum of the resulting copolymer has no peak as-
signed to vinyl protons. This ®nding reveals that the
polymerization proceeds by a cleavage carbon±carbon
double bond. The number average molecular weight was
determined as 3600 by the GPC method.
 S. Masuda et al. / European Polymer Journal 37 (2001) 705±710 707

copolymerizations at 20°C and 40°C are fast in its initial

stage, become gradually sluggish with time, and appear
to come to a halt before all monomers are consumed.
The time course is not linear in all cases.
Table 2 lists the e€ect of additives on the spontaneous
copolymerization. The copolymerization is not acceler-
ated by the addition of AIBN, and inhibited by BQ. On
the other hand, it is accelerated by boron tri¯uoride
ethyl etherate and inhibited by butylamine. Although
the e€ect of boron tri¯uoride and acetic acid suggests
ionic mechanism, the spontaneous copolymerization is
accelerated by water, which is a typical inhibitor of ionic
polymerization. It is dicult to draw conclusions about
reaction mechanism from these data alone.
In order to determine microscopic acid dissociation
constants for 1:1 copolymer of AA and 4VP, it is nec-
essary to prepare the 1:1 copolymer of methyl acrylate
(MA) and 4VP as well. The spontaneous copolymer-
ization of AA with 4VP at 40°C, and the AIBN-initiated
copolymerization of MA with 4VP at 60°C were carried
Fig. 1. Relationship between rate and monomer concentration out. Monomer±copolymer composition curves are shown
for the spontaneous copolymerization of AA and 4VP at 40°C in Fig. 2. For the AA±4VP system, the copolymer with
for 30 min ‰AAŠ=‰4VPŠ ˆ 1:04. 1:1 composition was obtained over a wide range of
monomer ratios in the feed. That is to say, the sponta-
neous copolymerization takes place alternatingly. The
Table 1 formation of alternating copolymer implies participa-
Relationship between conversion (%) and temperature for the
tion of complex to the copolymerization. As indicated in
spontaneous copolymerization of AA with 4VP in ethanola
Fig. 3, the UV absorption has the maximum value at
Time Temperature (°C) equimolar concentration of AA and 4VP, which is sug-
(min) 0 10 20 30 40 gestive to the formation of the 1:1 monomer complex.
5 1.5 0.6 1.2 5.6 9.5 This complex does not seems to be a charge transfer
10 2.1 4.0 13.6 18.1 18.6 (CT) complex, but an ionic pair of AA anion and 4VP
15 4.4 14.3 21.6 23.2 23.6 cation, for no CT complex of MA and 4VP is observed,
20 8.2 24.9 26.1 25.9 28.2 and migration of proton from a carboxyl group to ni-
25 15.2 27.1 29.7 29.3 31.7 trogen atom of pyridine ring is easy. For the MA±4VP
30 19.3 29.8 32.3 30.9 32.3 system, monomer reactivity ratios rMA ˆ 0:09 and
a
‰AAŠ ˆ 2:92 mol lÿ1 and ‰4VPŠ ˆ 2:80 mol lÿ1 . r4VP ˆ 1:13 were obtained by Kelen±T ud}os method [23].
The 1:1 copolymer was prepared on the basis of
Table 1 shows relationship between the time and monomer reactivity ratios obtained. The alternating
conversion for the spontaneous copolymerization. The copolymer of AA and 4VP and 1:1 copolymer of MA
reaction proceeds even at 0°C. The copolymerizations at and 4VP are abbreviated as PACV and PMCV, re-
0°C and 10°C have a short induction period. The spectively.

Table 2
E€ect of additives on the spontaneous copolymerization of AA with 4VP
[AA] (mol 1ÿ1 ) [4VP] (mol 1ÿ1 ) Additive (mol 1ÿ1 ) Temperature (°C) Time (min) Conversion (%)
1.94 1.86 None 40 30 18.8
1.94 1.86 AIBN (0.01) 40 30 19.8
1.94 1.86 BQ (0.01) 40 30 20.6
2.92 2.80 None 0 20 11.3
2.92 2.80 BF3 ethyl eltherate (0.05) 0 20 21.0
2.92 2.80 Butyllithium (0.05) 0 20 9.0
2.92 2.80 Water (1.0) 0 20 23.0
2.92 2.80 Acetic acid (1.0) 0 20 34.6
2.92 2.80 Butylamine (1.0) 0 20 0
708 S. Masuda et al. / European Polymer Journal 37 (2001) 705±710

Fig. 4. A schematic representation of macroscopic and micro-

Fig. 2. Monomer±copolymer composition curves for the AA± scopic ionization equilibria of the AA±4VP copolymer.
4VP ( ) and MA±4VP (d) systems.

and PMCV were titrated with potassium hydroxide.

Macroscopic acid dissociation constants K1 ˆ 4:90 
10ÿ4 , K2 ˆ 1:95  10ÿ12 , and K3 ˆ 4:47  10ÿ4 were
evaluated from the relationship between the degree of
ionization and pH values.
In addition, the relations between macroscopic and
microscopic dissociation constants are as follows. By
assuming k2 ˆ K3 , microscopic constants
‰H‡ Š‰IIŠ ‰H‡ Š‰IIIŠ
k1 ˆ ; k2 ˆ ;
‰IŠ ‰IŠ

‰H‡ Š‰IVŠ ‰H‡ Š‰IVŠ

k12 ˆ ; k21 ˆ ;
‰IIŠ ‰IIIŠ

‰H‡ Šf‰IIŠ ‡ ‰IIIŠg

K1 ˆ ˆ k1 ‡ k2 ;
‰IŠ

1 ‰IIŠ ‡ ‰IIIŠ 1 1
ˆ ˆ ‡ ;
K2 ‰H‡ Š‰IVŠ k12 k21

Fig. 3. Continuous variation method for AA±4VP system.

Spectra were measured in ethanol at 295 nm. ‰H‡ Š2 ‰IVŠ
K1 K2 ˆ ˆ k1 k12 ˆ k2 k21 ;
‰IŠ

3.2. Macroscopic and microscopic acid dissociation ‰IIŠ k1 k21

Fig. 4 gives a schematic representation of micro-
scopic ionization equilibria of PACV, together with
more familiar macroscopic stepwise acid distribution
sequence.
Various methods are known for the determination of
microscopic acid dissociation [24±28]. Titration method
was used in this study. As described in Section 2, PACV
Kt ˆ ˆ ˆ
‰IIIŠ k2 k12
(k1 , k12 and k21 ) for PACV are calculated according to
the above equations.
This assumption is generally accepted because the
dissociation equilibria of PMCV are essentially attrib-
uted to deprotonation of pyridinium ion. Table 3 sum-
marizes acid dissociation constants and tautomeric
 S. Masuda et al. / European Polymer Journal 37 (2001) 705±710
Table 3
Macroscopic and microscopic acid dissociation constants
Sample Dissociation constant
pK1
1:1 Copolymer of AA and 4VP 3.31
Monomer mixture of AA and 4VP 4.52
Mixture of AA and 4VP homopolymers 3.75
constants (Kt ). The neutral form of PACV is more stable
than its zwitterionic form in neutral region because of
Kt < 1. On the other hand, 1:1 monomer mixture and
1:1 homopolymer mixture are in reverse.
The distribution of the microscopic forms as a
function of pH is of interest, in connection with pH-
dependence of biologically and physiologically active
amino acids and pyridine derivatives. Figs. 5±7 show the
Fig. 5. pH-distribution curves for the microscopic forms of the
alternating copolymer of AA and 4VP.
Fig. 6. pH-distribution curves for the microscopic forms of the
mixture of AA and 4VP monomers.
709
Kt
pK2 pk1 pk2 pk12 pk21
11.71 4.37 3.35 10.65 11.67 0.0955
5.47 4.27 4.96 5.27 5.03 1.75
6.24 3.97 4.17 6.02 5.83 1.58
Fig. 7. pH-distribution curves for the microscopic forms of the
mixture of AA and 4VP homopolymers.
fractional concentrations of the individual microscopic
forms. The relative concentrations were calculated using
the relation equations of micro-constants and hydrogen
ion concentration. The concentration of the protonated
form of the alternating copolymer, which exists exclu-
sively in the lower pH range, decreases with increasing
pH value and fully vanishes at pH  6, while the de-
protonated form begins to appear around pH ˆ 9. The
zwitterionic and neutral forms coexist over a wide range
of pH, and the latter form is predominant regardless of
pH value. For the monomer and homopolymer mix-
tures, on the other hand, the zwitterionic and neutral
molecule forms coexist at a limited range of pH around
5 and the former is predominant.
It is generally known in amino acids, such as glycine
[1] and lysine [2], that zwitterionic form is more stable
than neutral molecule form in neutral region. In fact,
the behavior of acid dissociation in aqueous solution
is consistent with general tendency of amino acids in
both systems of monomer and homopolymer mixtures,
whereas the neutral form is predominant in PACV. The
reason for the preponderance of the neutral form is not
clear.
When two monomers (AA and 4VP) are mixed,
about half of molecules changes to the ionic form. The
ion pair or ion complex of AAÿ and 4VP‡ may play an
important role in the spontaneous copolymerization.
710 S. Masuda et al. / European Polymer Journal 37 (2001) 705±710
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