European Polymer Journal 37 (2001) 1165±1173

www.elsevier.nl/locate/europolj

Polymerization of methyl methacrylate and styrene in presence

of phthalides
Yu.I. Puzin a,b,*, A.E. Egorov a, V.A. Kraikin a
a
Institute of Organic Chemistry of the Ufa' Branch of Russian Academy of Science, Prospekt Octyabrya 69, 450054 Ufa,
Russian Federation
b
Ufa' State Petroleum Technological University, Kosmonavtov Street 1, 450062 Ufa, Russian Federation
Received 26 April 2000; received in revised form 5 September 2000; accepted 9 October 2000

Abstract
The radical polymerization of vinyl monomers (methyl methacrylate, styrene) has been investigated in the presence
of phthalides of di€erent structure.
It is shown that the phthalides containing halogen atoms are, ®rst of all, chain-transfer agents. The values of chain-
transfer constants to them have been determined. It was found that the presence of chlorine atom bounded directly with
carbon of phthalide cycle in a phthalide molecule results in considerable growth of chain-transfer constant value to
phthalide. If the halogen is connected with aromatic group of phthalide, phthalide is a weak chain-transfer agent and
the phthalide cycle is not included in polymer molecule. It is shown that the phthalides containing mobile atoms of
hydrogen can take part both in chain-transfer and in initiating system formation with the initiator. The function of
phthalide is determined by structure of phthalide, monomer and initiator. The mechanism of phthalide participation in
polymerization has been discussed. The solutions of poly-MMA containing phthalide groups in macromolecules in
concentrated sulfuric acid are intensively colored. This fact was used for quantitative determination of phthalide cycles
in a polymer chain. It has been found that when UV irradiated the bulks of poly-MMA ¯uoresce and phosphoresce in a
visible part of spectrum. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Radical polymerization; Methyl methacrylate; Styrene; Phthalides; Luminescence

1. Introduction Heterocyclic aromatic polymers are known to have a

The problem of direct synthesis of polymers with
functional groups in main and/or side chains of macro-
molecule attracts attention of many researchers. Syn-
thesis of polymers containing monomeric or functional
groups of di€erent structures is of a special interest. So,
when creating electroconductive polymers good results
have been achieved when heteroaromatic polymers, ex-
actly, poly(arylene phthalides) had been used [1].
*
Corresponding author. Address: Institute of Organic
Chemistry of the UfaÕ Branch of Russian Academy of Science,
Prospekt Octyabrya 69, 450054 Ufa, Russian Federation.
E-mail addresses: puzin@anrb.ru, puzinyu@diaspro.com
(Yu.I. Puzin).
number of valuable properties, for example, high ther-
mostability. Usually, these polymers are obtained by
polycondensation. However, high thermostability com-
bines with high glass transition and ¯ow points and also
with poor solubility in the most part of organic solvents.
On the contrary, many of vinyl polymers, in particular,
polyacrylates have low points of glass transition and
¯ow and high solubility. Usually, they are synthesized
by radical polymerization.
It is logical to expect that heterocyclic aromatic
groups entered in macromolecule keep a part of the
properties. Phthalides are of a special interest. It is
known [2] that a number of substituted diphenyl
phthalides and lactams are colored intensively at high
pressure in combination with shift stresses. Compounds
containing phthalide cycle are colored in concentrated

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 2 3 8 - X
1166 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173
sulfuric acid [3] also and it can serve as a method of their
qualitative and quantitative analysis. It is known also
that polymeric matrix can promote thermochromism
and in¯uence on luminescence properties of some com-
pounds [4]. However, few such examples are known.
Therefore, the introduction of heteroaromatic com-
pounds in acrylic polymers, ®rst of all, at stage of their
synthesis is a very actual task.
Phthalide introduction in polymer molecule by radi-
cal polymerization methods can be realized by means of
their participation in the chain-transfer and/or poly-
merization initiation reactions. In this connection the
phthalides containing halogen in molecule are of a spe-
cial interest because they are known as chain-transfer
agents. Phthalides containing mobile hydrogen atoms
are also interesting because C±H acids participate in the
formation of oxidation±reduction initiating systems in
combination with acyl (or aroyl) peroxides as well as in
chain-transfer process [5].
This article presents the results of methyl methacry-
late (MMA) or styrene polymerization in presence of
phthalides containing halogens (compounds I±VII, IX)
and/or mobile hydrogen atoms (compounds VIII±XI)
are presented as well as some properties of the polymers
obtained.
2. Experimental
2.1. Materials
MMA and styrene were puri®ed from stabilizer by
frequent washing with 5±10% KOH (in water) then with
water. Monomers were dried over CaCl2 and molecular
 and distilled before use. Boiling points
sieves (3 A)
are 42°C at 100 mm (MMA) and 70°C at 60 mm
(styrene).
Azo-bis-iso-butyronitrile (AIBN) and benzoyl per-
oxide (BP) were recrystallized from methanol and dried
at room temperature in vacuum up to constant weight.
Phthalides I±VII, IX±XI were obtained by Friedel±
Crafts method [6,7]. Some data on their synthesis and
puri®cation are given in Table 1. Substance VIII was
used of commodity standard (Aldrich, USA, N P3,960-
5); it was recrystallized from methanol before applying;
m.p. 73°C.
Phthalides II, IV, V, VIII±XI are soluble in MMA in
limited quantity.
2.2. Procedures
The polymerization kinetics was studied dilatomet-
rically. Polymer after 5% conversion was precipitated
in methanol or hexane and dried; its molecular weight
was measured by viscosimetry in benzene at 25  0:05°C
using the following equations [8],
‰gŠ ˆ KM a ; K ˆ 0:94  10 4 ; a ˆ 0:76 …poly-MMA†;
K ˆ 2:70  10 4 ; a ˆ 0:66 …poly-St†;
with [g] in dl/g.
The relative chain-transfer constants for phthalides
CS were calculated using Mayo equation [9]:
1 1 ‰SŠ
ˆ ‡ CS
Pn Pn0 ‰MŠ
where Pn and Pn0 are the average degrees of polymer-
ization in presence and absence of the phthalides,
accordingly; [S] and [M] are concentrations of the
phthalide and monomer.
Molecular-weight distribution (MWD) curves were
registered on the gel-chromatograph ``CH-ZH 1302''
(Russia). Columns ®lled with ``Waters'' styrogel with
 were used; chloroform was used as a
pore size 102 ±106 A
solvent, feed speed was 1 ml/min; temperature was 25°C.
The columns were calibrated by polystyrene standards
from the ®rm Aldrich (USA).
Before determination of phthalide amount in poly-
mers they were extracted many times by methanol in
Soxhlet apparatus as phthalides I±XI are well soluble in
methanol.
The UV spectra of poly-MMA solution in sulfuric
acid were registered on spectrometer ``UV±VIS±NIR
3100'' (Shimadzu, Japan).
 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173 1167

Table 1
Synthesis and some properties of phthalidesa
Phthalide Reagents Procedure Some properties
I (a) Phthalic acid anhydride (0.6 mol) (a) Heating at 60°C during 1 h White crystalline powder
(b) AlCl3 (1.2 mol) (b) Adding to 1 kg ice and 50 ml 36% m.p. 57°C
(c) Benzene (1 mol) HCl
(d) SOCl2 (12.3 mol) (c) Precipitate ®ltering and washing
(d) Solution of precipitate in 7% KOH
(e) Boiling with active carbon
(f) Filtrating from carbon
(g) Neutralizing of ®ltrate with HCl
(h) Precipitate ®ltering and washing
(i) Crystallization and recrystallization
from ethanol
II (a) Phthalic acid anhydride (0.6 mol) As above for I White crystalline powder
(b) AlCl3 (1.2 mol) m.p. 167.5±168°C
(c) Diphenyl oxide (1 mol)
(d) SOCl2 (12.3 mol)

III (a) Phthalic acid dihalide (0.2 mol)
(b) AlCl3 (0.12 mol)
(c) Chlorobenzene (0.2 mol)
(d) Benzene (0.2 mol)
(a) Mixing at room temperature during White crystalline powder
1 day m.p. 171±172°C
(b) Distillation of reagent surpluses in
vacuum
(c) Adding to cooled water solution of
NaOH (3%)
(d) Precipitate ®ltering and washing
(e) Crystallization and recrystallization
from ethanol

IV (a) Phthalic acid dihalide (0.2 mol) As above for III White crystalline powder
(b) AlCl3 (0.12 mol) m.p. 158±159°C
(c) Chlorobenzene (0.41 mol)
V (a) Phthalic acid dihalide (0.2 mol) As above for III White crystalline powder
(b) AlCl3 (0.12 mol) m.p. 125±126°C
(c) Fluorobenzene (0.41 mol)
VI (a) Phthalic acid anhydride (0.6 mol) As above for I White crystalline powder
(b) AlCl3 (1.2 mol) m.p. 150.5±152°C
(c) Chlorobenzene (0.9 mol)
VII (a) Phthalic acid anhydride (0.6 mol) As above for I White crystalline powder
(b) AlCl3 (1.2 mol) m.p. 167±168.5°C
(c) Bromobenzene (0.9 mol)
IX (a) Phthalic acid anhydride (0.6 mol) As above for I White crystalline powder
(b) AlCl3 (1.2 mol) m.p. 147±148.5°C
(c) Fluorene (0.9 mol)
X (a) Phthalic acid dihalide (0.2 mol) As above for III White crystalline powder
(b) AlCl3 (0.12 mol) m.p. 250.5±252°C
(c) Fluorene (0.41 mol)
XI (a) Phthalic acid anhydride (0.6 mol) As above for I White crystalline powder
(b) AlCl3 (1.2 mol) m.p. 228±230°C
(c) Fluorene (0.9 mol)
a
Other properties are given in Ref. [7].
1168 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173

Luminescence and phosphorescence spectra were reg-

istered on spectro¯uorimeter ``MPF-4'' (Hitachi, Japan).

3. Results and discussion

3.1. Phthalides containing halogen atoms (I±VII)

It has been revealed that phthalides I±VII do not

practically in¯uence initial polymerization rate W0
(Table 2) when polymerization initiated by AIBN takes
place. W0 varies insigni®cantly (up to 7%) in the pres-
ence of substances II or IV±VII. The average polymer-
ization degree is notably reduced (Table 2). The weak
in¯uence of phthalides I±VII on W0 and considerable
in¯uence on the polymerization degree Pn indicates that
these compounds are mainly the chain-transfer agents.
The values of chain-transfer constants CS of these
phthalides are presented in Table 3. One can see that all
phthalides are more active chain-transfer agents than
benzene.
The values CS for I and II are close and higher no-
tably than that for III±VII. It can be conditioned by
higher activity of chlorine atom. It has been found [7,12]
that dual reactivity is characteristic for chemical reac-
tions of chlorine-containing phthalides and it is con-
nected with their two forms ± cyclic and open:
The ability of chlorine atom to migrate and higher
activity of acid halide as chain-transfer agent than that
of aromatics allow to propose the following mechanism
of chain-transfer to I and II (Scheme 1). Radical A (as
distinct from B) has a smaller activity in chain propa-
gation reaction owing to additional stabilization by
aromatic substituent R. The presence of biphenyl sub-
stituent (R ˆ Ph) in phthalide II causes more consider-
able stabilization of radical A and it is the reason for
some decrease of W0 in the presence of II as well as of
higher value of CS on II. It is proved by more anity of
biphenyl to radical than that of benzene [10].
Phthalides III±VII are not acid chloride (or pseudo
acid chloride) and have no mobile atom of halogen. The
values of CS for them are lower than that in the case of I
or II but the chain-transfer on III±VII proceeds much

Table 2
Polymerization of MMA at 60°C initiated by AIBN in presence of phthalides containing halogen
Phthalide Initiator concentration Phthalide concentration Polymerization rate Polymerization degree
[I]0  103 mol/l [S]0  103 mol/l W0  103 mol/l min Pn  10 3
I 3.65 0 13.25 3.80
167 13.12 3.25
250 13.07 1.21
500 13.16 1.00
II 3.65 10.0 12.70 3.21
20.0 12.97 2.73
30.0 13.15 2.43
III 3.65 120 13.15 3.65
240 13.19 3.04
480 13.31 2.34
IV 3.65 10.0 12.30 3.61
25.0 12.16 3.27
43.0 12.40 2.99
V 3.65 4.4 12.43 3.73
9.9 12.63 3.63
23.4 13.17 3.48
VI 2.00 0 9.20 6.52
100 9.57 6.49
417 9.53 6.39
VII 2.00 100 9.31 6.49
150 9.26 6.46
 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173 1169

Table 3
Chain-transfer constants CS on phthalides I±VII at MMA po-
lymerization (60°C)
Compound CS  102
I 1.44
II 4.49
III 0.67
IV 1.22
V 0.93
VI 0.0060
VII 0.0082
Benzene 0.00075a
Chlorobenzene 0.0015a
Fluorobenzene 0.0009a
a
From Refs. [10,11]

Scheme 2. Process of chain transfer on phthalides with aryl

halide substituents.

well as I and II in concentrated H2 SO4 assume bright

color (Table 4) characteristic for phthalides [3].
Phthalides VI and VII contain aryl halide groups
only and there are no other chain-transfer centers.
Really, the values of CS on them and on chlorobenzene
are of the same order (Table 3). It is known also that
values CS for chloro- or bromobenzene are close [10]. It
Scheme 1. Process of chain transfer on 3-chlorophthalides. means that chain-transfer with participation of these
phthalides proceeds according to way (1) (Scheme 2) and
does not result in insertion of their molecules in poly-
more actively than on ¯uoro- or chlorobenzene (Table mer. It is con®rmed by the fact that solutions of poly-
3). MMA synthesized in their presence in concentrated
It is known [10] that the chain-transfer to aryl halides
does not result in rupture of the C±Hal bond. On the
other hand, the presence of several aromatic substituents
bonded with carbon of phthalide cycle facilitates its Table 4
Colors of solution in sulfuric acid of poly-MMA synthesized in
rupture with aromatic ring. So, the chain-transfer to
the presence of phthalides
phthalides III±VII can be presented as follows (Scheme
2). This scheme takes into account that chain-transfer to Phthalide Wavelength of Color of solution
VI or VII proceeds in an aromatic ring bonded with absorption k (nm)
halogen and that the ortho-position is more probably I 402 Yellow
subjected to radical attack [10]. II 307 No colored in VIS
The direction (1) (Scheme 2) presents the generally III 318 Yellow
441
accepted mechanism of chain-transfer to aryl halides
IV 307 Yellow
[10,13]. But in case of phthalides III±V the breakdown of
481
tertiary carbon bond seems to be rather possible (di- V 326 Lemon-yellow
rection 2 in Scheme 2) because the radical D is stabilized 455
by aromatic substituents. Moreover, the migration of VIII 322 No colored in VIS
substituent from carbon of phthalide cycle was noticed IX 307; 396 Cherry-red
by many researchers [7,12]. 488; 509
The probability of chain-transfer in accordance with X 312; Blue
((2), Scheme 2) is con®rmed by the presence of phtha- 456; 581
lide-groups in polymer molecule. The solutions of poly- XI 322; 395 Cherry
509
MMA obtained in the presence of phthalides III±V as
1170 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173

sulfuric acid are not colored though the solutions of VI
or VII in H2 SO4 are brightly colored.
Value of CS for phthalide III containing one chloro-
phenyl group is less than that for phthalide IV with two
such groups. Probably, it can be explained by relative
increase of electronic density on benzene ring owing to
positive mesomeric e€ect of chlorine atom making easier
the radical attack to the ring. The similar e€ect of ¯u-
orine is less [14], therefore, phthalide V reacts weaker
with radical and it results in decrease of CS value.
3.2. Phthalides containing mobile atoms of hydrogen
(VIII±XI)
If AIBN is used as initiator, the initial rate of poly-
merization in presence of VIII is slightly reduced at ®rst,
then it grows. But the initial value observed in absence
of VIII is not reached (in the investigated interval of
VIII concentration) (Table 5). The polymerization de-
gree varies similarly and it indicates possible participa-
tion of VIII in polymerization initiation [10,15]. In this

Table 5
Polymerization of MMA or styrene at 60°C in presence of phthalides VIII±XI
Phthalide Monomer Initiator Initiator concen- Phthalide concen- Initial polymeriza- Polymerization
tration [I]0  103 tration [S]0  103 tion rate W0  103 degree
mol/l mol/l mol/l min Pn  10 4
VIII MMA AIBN 1.00 0 5.42 0.63
0.25 4.60 1.59
0.50 4.47 1.65
0.75 4.41 1.81
1.00 4.58 1.71
1.50 4.75 1.57
BP 1.00 0 4.11 1.43
0.25 4.77 1.24
0.50 6.11 1.26
0.75 7.19 1.29
1.00 9.64 1.34
1.50 12.33 1.39
IX MMA AIBN 1.00 7.50 6.00 0.24
15.00 4.03 1.74
BP 1.00 7.50 4.07 1.11
15.00 4.03 1.74
Styrene AIBN 3.65 0 2.72 0.31
10.00 2.74 0.13
24.90 2.81 0.05
I MMA AIBN 3.65 0 13.25 0.38
167 13.12 0.33
250 13.07 0.12
500 13.16 0.10
X MMA AIBN 1.00 2.73 6.46 1.09
5.45 6.04 0.93
10.90 6.05 0.84
BP 1.00 2.73 4.50 0.91
5.45 5.92 1.00
10.90 7.84 1.12
Styrene AIBN 3.65 5.76 2.82 0.21
11.55 2.80 0.16
23.10 2.84 0.13
XI MMA AIBN 1.00 3.22 6.55 1.12
6.43 6.22 0.94
BP 1.00 3.22 4.30 1.05
6.43 5.31 1.07
Styrene AIBN 3.65 2.15 2.77 0.30
4.30 2.84 0.28
8.60 2.81 0.25
 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173
case it is not possible to estimate the participation of the
compounds in chain-transfer process.
If BP is used as initiator, the addition of VIII results
in the growth of W0 accompanied at ®rst by decrease
and then by increase of polymerization degree (Table 5).
The analogous change of W0 and Pn in case of increase
of VIII concentration means that phthalide VIII par-
ticipates in formation of redox initiating system (ROS)
with peroxide.
The presence of phthalide IX in MMA results (if
AIBN is initiator) in some growth of W0 and simulta-
neously considerable decrease of Pn (Table 5). Probably,
phthalide IX participates both in initiation and in chain-
transfer processes but the latter dominates. Based on
decrease of molecular mass of poly-MMA versus IX
concentration, the value of CS to IX was calculated to be
equal to 0.190. It means that IX is very active as chain-
transfer agent. For comparison, the data on polymer-
ization in the presence of I are presented in Table 5. One
can see that chloro-containing phthalide having no ¯u-
orene groups decreases the polymerization degree and
does not e€ect W0 and participate in chain-transfer with
CS ˆ 0:0144. Chain-transfer to I can be connected with a
high activity of chlorine atom (it was discussed above).
Therefore, the mechanism of chain-transfer to IX can
be shown as follows (Scheme 3). Chain-transfer to I can
be realized only by directions (3.1) and (3.2), and the
®rst one is more probable. Radical E (in contrary to F) is
less active in chain propagation owing to additional
stabilization by aromatic substituents and it facilitates
the radical formation and its interaction with growing
macroradical r .
Fluorene group is a new active center of chain-
transfer. For example, CS value on ¯uorene during
styrene polymerization at 60°C is 0.075, that is 4170
Scheme 3. Chain transfer on 3-chloro-3-¯uorenyl-phthalide.
1171
times as much as that on benzene [13]. Phthalide XI
unlike IX contains only one ¯uorene group and the rate
of MMA polymerization initiated by BP increases in
the presence of XI (Table 5). It should be noted that
aromatic carboxylic acids, for example, benzoic acid, do
not e€ect W0 and are very weak chain-transfer agents
[16]. Phthalide IX contains both ¯uorene and chloride
groups. In its presence the polymerization rate does not
practically change and polymerization degree grows
(Table 5).
Thus, the in¯uence of ¯uorene phthalides on process
of polymerization depends on structure of monomer and
initiator. When discussing the mechanism of their par-
ticipation in the process, it is necessary to take into ac-
count the following.
(1). There is no interaction between phthalide and
initiator, the in¯uence of phthalides IX±XI does not
depend on a structure of the initiator, but it is not so.
(2). If we assume that the rate of termination de-
creases, the structure (or activity) of macroradical should
change. But it is not connected with structure of the
initiator, but it is not so.
(3). The kinetic scheme of radical polymerization is
based on several assumptions. One of them assumes that
the chain-transfer does not change the activity of a
radical [17]. As a result of chain-transfer the radicals
distinguished from primary radicals by the structure will
be formed. Their interaction with a molecule of a
monomer is characterized by the same (or greater)
constant of chain propagation rate, as interaction of a
primary radical. Therefore agent of chain-transfer
should not directly in¯uence the activity of a macro-
radical (probably, except special cases of complexing).
Above mentioned allows to conclude, that phthalides
IX±XI increase the initiator destruction in radical poly-
merization, that is form redox systems. Probably, it is
connected with mobility of hydrogen atom in phthalide
CH2 group.
This supposition is con®rmed by in¯uence of phtha-
lide X on polymerization process. Phthalide X contains
two ¯uorene groups and must react actively with per-
oxidic initiator. Really, the rate of polymerization in-
creases strongly in the presence of phthalide X but
polymerization degree decreases (Table 5).
Earlier we mentioned [5,18] that the compounds
containing mobile hydrogen atoms react with peroxide
or azo-initiator resulting in ROS. Also we paid attention
to in¯uence of the monomer on polymerization initia-
tion. The reaction between initiator and C±H acid in-
tensi®es in MMA but slackens in styrene. Analogous
e€ect is observed during polymerization carried out
in the presence of phthalides (Table 5). When concen-
tration of IX or X increase the rate of styrene poly-
merization changes insigni®cantly, but polymerization
degree of polystyrene is strongly decreased. It means
that these phthalides are chain-transfer agents with
1172 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173
Scheme 4. Reaction of benzoyl peroxide and C±H acids.
constants CS ˆ 0:532 (for IX) and 0.170 (for X) and
0.082 (for XI) at 60°C. It is important that the value of
CS for X is almost equal to the doubled value of CS for
¯uorene (0.075) as well as for XI.
The comparison of CS value for IX or X con®rms
the conclusion that the halogen bond with carbon of
phthalide cycle is the most active one in chain-transfer.
The general scheme of ¯uorene-containing phthalide
participation in initiation of polymerization can be
presented as follows (Scheme 4).
It is known that polarity of monomer in¯uences the
donor±acceptor complex formation [19]. Therefore for-
mation of complex G (Scheme 4) proceeds actively in
MMA but weakly in styrene. Therefore, C±H acids do
not practically e€ect the rate of styrene polymerization.
If the acidity of C±H acids grows, however, the part of
phthalide in radical polymerization changes because of
formation of complex G. It was demonstrated by us
taking as examples the more active C±H acids (diethyl
malonate or acetyl acetone) than ¯uorene [5].
Molecules of poly-MMA contain the phthalide
groups. Really, solutions in concentrated sulfuric acid of
polymers obtained in presence of VIII±IX are colored
(Table 4) which is typical for phthalides [3]. We used this
method for quantitative determination of phthalide
Table 6
Luminescence of poly-MMA bulks synthesized in presence of phthalides
Phthalide Wavelength of exciting, k (nm)
I 378
II 375
III 372
IX 375
XI 375
groups in poly-MMA macromolecule. Before analysis
the polymers were many times extracted by methanol in
Soxhlet apparatus.
The spectrum of solution of poly-MMA synthesized
in the presence of X in conc. H2 SO4 contains the same
absorption bands which are characteristic for solution of
X in conc. sulfuric acid (Table 4). The calibration de-
pendence of optical density of X in conc. H2 SO4 on its
concentration was preliminarily obtained and extinction
coecient e was calculated (e ˆ 11000 for k ˆ 581 nm).
The quantity of phthalide groups in macromolecule
was 1/1900 (mole per mole of monomer unit). The values
of poly-MMA molecular weight were calculated on the
base of gel-chromatography (number-average molecular
weight Mn ˆ 340 000) and viscosimetry (viscosity-aver-
age molecular weight Mg ˆ 365 000) data. Therefore,
there are 1.92 phthalide groups in a polymer molecule
(1.80 according to viscosity data). It means that phtha-
lide groups can be not only at the end of macromolecule
chain but also inside it. Probably, two ¯uorene groups of
the phthalide X take part in polymerization initiation so
the insertion of phthalide group can be ``inside'' the
molecule. Really, the participation of two ¯uorene
groups in chain-transfer was marked above which indi-
cates about their relative independence from each other.
3.3. Optical properties of polymers obtained
Bulks of poly-MMA synthesized in the presence of
phthalides have luminescence in visible spectral part at
UV irradiation (Table 6). Typical spectra of excitation
and luminescence are shown in Fig. 1. Moreover, poly-
MMA bulks obtained in the presence of II or III
phosphoresce at UV irradiation (Table 6).
It is known [20,21] that two components of emission
are present in the luminescence spectra of poly-MMA
such as molecular (monomeric) and excimeric. The
emission of excimer type is ascribed to the aggregates of
luminophore with excimer-forming centers. The latters
Wavelength of emission, k (nm) Time of half decrease of
phosphorescence intensity,
s1=2 , s
480 ±
517
480 12
510
473 15
508
477 ±
510
473 ±
508
 Yu.I. Puzin et al. / European Polymer Journal 37 (2001) 1165±1173
Fig. 1. Luminescence spectra of poly-MMA bulk containing
phthalide I. 1 ± Spectra of excitation; 2 ± Spectra of emission.
are both pre-formed con®rmations of polymer chains
suitable for formation of excimers and the chain frag-
ments (segment) which have too low energy barrier to
attain excimer con®guration.
Values of wavelengths of excitation or emission are
very close for polymers obtained in the presence of dif-
ferent phthalides. So, the emission of molecular type
connected with the presence of phthalide cycle in poly-
meric matrix is more probable. Phosphorescence may be
induced by excimer centers in polymer [20±22]. Thus, the
polymer structure must have e€ect on phosphorescence.
So, polystyrenes obtained in analogous conditions do
not have phosphorescence at UV irradiation.
Acknowledgements
This work is supported by Russian fund of basic
researches (RFBR), No. 98-03-33322.
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