Molecular Catalysis xxx (xxxx) xxx

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Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis

Study of the Cu[I]/Cu[II] catalytic system in 2,6-dimethylphenol

polymerization to poly(phenylene oxide)
Sebastian Firlik a, *, Dorota Alichniewicz-Kalinowska b, Wincenty Skupiński c
a
Łukasiewicz Research Network – Industrial Chemistry Institute, Rydygiera 8 str., 01-793 Warsaw, Poland
b
Former employee at the Łukasiewicz Research Network – Industrial Chemistry Institute, Rydygiera 8 str., 01-793 Warsaw, Poland
c
Emeritus professor at the Łukasiewicz Research Network – Industrial Chemistry Institute, Rydygiera 8 str., 01-793 Warsaw, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: The study of Allan S. Hay catalytic systems containing copper[I] and copper[II] complexes, ie. CuBr/dbeda
POLY(phenylene oxide) (where dbeda = N, N’-di-(t‑butyl)ethylenediamine), Cu2O/Br2/dbeda CuBr2/dbeda and CuCO3/Br2/dbeda in the
Oxidative polymerization polymerization of 2,6-dimethylphenol(2,6-DMP) to poly(phenylene oxide) (PPO) was presented. In the presence
Mechanism of the 2,6-dimethyphenol poly­
of bromine in the amount of 4.5 Br2/Cu, the copper[II] catalysts formed the greater number of polymerization
merization
2,6-dimethylphenol
centers. The values of the molar mass as well as its distribution depended on the 2,6-DMP/Cu molar ratio and the
reaction time. Polymer with the higher molar mass was obtained at the molar ratio 2,6-DMP/Cu = 1000 and with
the use of the copper[I] catalyst. By increasing the 2,6-DMP/Cu ratio to 1800, polymer with the lower molar
mass was prepared. The reverse effect was observed for the copper[II] catalyst. The mechanism of 2,6-DMP
polymerization to PPO was proposed in presence of the used catalysts. Also, the role of the bromine excess in
the process was explained. In this mechanism the copper system Cu[I]⇄Cu[II] is responsible for the formation of
oxygen and para-carbon radicals which are the starting molecules to launch the polymer synthesis. The "bromine"
system reversibly provides the Br2 molecule to brominate 2,6-DMP. The resulting 4‑bromo-2,6-dimethylphenol
forms a carbon radical in the reaction with copper[I] complex.

1. Introduction The Cu [I]/Cu[II] reaction constitutes an important step in an Atom

The acceptance of an electron by Cu2+ion, thus transforming into the
Cu1+ +0.15 V ion is privileged. The reverse reaction of Cu1+ to Cu2+ will
amount to − 0.15 V and will require additional energy. These energies
remain relatively low. The difference results from the fact that Cu1+ ion
has the 3d10 electron configuration, i.e. filled 3d orbitals, while Cu2+ ion
has the 3d9 configuration and therefore is less stable [1]. The low energy
of these transformations ensures relatively favorable catalytic trans­
formations requiring a single-electron, i.e. a radical-based process [2,3,
4,5,6].
Such transformations take place in the catalytic cycle of trans­
formations of Pd[II] complexes in the reaction of adding water to olefins,
i.e. in the Wacker reaction. This reaction is industrially important; in its
catalyzed route Pd[II] is reduced to Pd[0] and the stoichiometric CuCl2
molecules present in this process, restore the active Pd ion[II] by
transferring one chlorine to one Pd[0]. The resulting Cu[I] cations
recreate CuCl2 by oxidative chlorination with HCl. The same catalytic
transformations are taking place in diene hydrocyanation [2,3,4].
transfer radical polymerization (ATRP), which involves the formation of
carbon radicals from adequate alkyl and aromatic halides. LnCu[I]X +
RX → LnCu[II]X2 + R•, where L = ligand, X = halogen, R = alkyl, aro­
matic ring. These radicals initiate radical polymerizations to form
various products with the required composition and architecture [5].
Another important process involving the Cu [I]/Cu[II] trans­
formation is the poly(2,6-dimethyl-1,4-phenylene ether) synthesis [6].
Poly(2,6-dimethyl-1,4-phenylene ether) or poly(phenylene oxide)
(PPE, PPO) [21,22] - trademark NORYL™ is a commercially important
thermoplastic resin manufactured by SABIC. PPO is often blended with
thermoplastic resins e.g. polystyrene, polyopropylene [15] and widely
used in many industrial applications e.x. in the automotive industry
[23], computer and television casings [24].
It’s synthesis by CuCl/pyridine complex was discovered by Allan S.
Hay [16,17] whose works on 2,6-dimethylphenol (2,6-DMP) polymeri­
zation constitute the core of the research on PPO synthesis both in the
laboratory and industrial scale.
The most important factors influencing PPO synthesis are

* Corresponding author.
E-mail addresses: sebastian.firlik@ichp.pl (S. Firlik), wskupinski@ch.pw.edu.pl (W. Skupiński).

https://doi.org/10.1016/j.mcat.2021.111628
Received 5 March 2021; Accepted 5 May 2021
2468-8231/© 2021 Elsevier B.V. All rights reserved.

Please cite this article as: Sebastian Firlik, Molecular Catalysis, https://doi.org/10.1016/j.mcat.2021.111628
S. Firlik et al. Molecular Catalysis xxx (xxxx) xxx

composition and the molar ratio of the catalytic system components (e.x.
amine/Cu molar ratio), the molar ratio of 2,6-DMP/Cu and the used
solvent [16,25]. Various amines are used as a ligand for copper e.x.
diethylamine, dibutylamine, N, N, N’, N’-tetramethylethylenediamine
[16], morpholine [25]. However, the most effective is CuBr/dbeda/HBr
system. It permits conduct the reaction at the molar ratio of 2,6-DMP/Cu
> 1000 [12]. The so-called "bromine source" constitutes the essential Scheme 1. Copper(II) bromide and 4‑bromo-2,6-dimethylphenol formation.
part of this system, by stabilizing the copper complexes and having
crucial role in the mechanism of polymerization route. These sources
include, for instance, Br2, bromide salts and 4‑bromo-2,6-DMP [8,13,
14].
To obtained high molar mass PPO polymerization is carried out in
organic solvent, like toluene, chlorobenzene [16,25,26,27]
Mechanism of 2,6-DMP polymerization is not clarified yet. It is
believed, that the polymer growth is based on the formation of phenoxy
and aryl radicals [7,8,9,10]. Phenoxy radicals are formed via the reac­ Scheme 2. Copper(I) bromide and 4‑bromo-2,6-dimethylphenol formation.
tion with ortho-alkyl substituted phenols, with Cu[II] ions [8,10,11].
These radicals alone can initiate radical polymerization, or form Ar-O-Ar
bonds [11]. In demonstrated mechanisms of synthesizing PPO in pres­
filtered off. After filtration, the precipitate turned its color into light
ence of CuCl2 complexes, this radical substitutes the hydrogen in a
green. The solid was then washed with hexane (turned turquoise) and
phenolic ring in para position, thus forming the C–O-C bond between
dried under oil pump vacuum at room temperature. A gray-green
two phenolic rings with the reduction of Cu[II] to Cu[I] [7]. Carbon
product was obtained with the yield of 93.5%. Elemental analysis
radicals are formed, inter alia, in the reaction of alkyl or aryl halides
showed (average) 37.82% C, 7.5% H and 8.83% N [12].
with Cu[I] complexes, as reported previously [5].
CuCO3/Br2/dbeda and Cu2O/Br2/dbeda: The CuCO3 used for the
The aim of this study was to investigate and compare the activity of
reaction was dried at 120 ◦ C for 1 hour, methanol was distilled from
the A.S. Hay catalytic systems in PPO synthesis. In studies CuBr/dbeda,
CaH2. 4.81 g (39.37 mmol) of 2,6-DMP was dissolved in methanol.
Cu2O/Br2/dbeda, CuBr2/dbeda and CuCO3/Br2/dbeda systems were
Subsequently, 0.55 g (2.49 mmol) CuCO3 (0.35 g, 2.45 mmol Cu2O) was
used. The influence of the 2,6-DMP/Cu molar ratio and the polymeri­
added while stirring. The prepared solution of 3.15 g (19.71 mmol)
zation time on PPO yield and its molar mass were investigated. More­
bromine in 5 ml methanol was added to the mixture which was cooled
over, the new radical mechanism of the 2,6-DMP polymerization toward
vigorously and stirred until a clear solution was obtained. The solution
PPO synthesis was proposed.
was filled up with methanol to 50 mL [13].
The stoichiometry of the reactions taking place are presented on the
2. Experimental section
schemes below.Scheme 1 and Scheme 2.
The end products involve copper(I) and copper(II) bromides,
2.1. Reagents and materials
respectively, as well as 4‑bromo-2,6-dimethylphenol (the molar ratio of
4-Br-2,6-DMP/Cu = 8). In 1 ml of the diluted solution 0.05 mmol of Cu
2,6-dimetylphenol (2,6-DMP, Sigma Aldrich, purity > 99%,),
will be found and 8-fold excess of bromo‑subsituted monomer.
4‑bromo-2,6-dimethylphenol (4-Br-2,6-DMP, Sigma Aldrich, purity
97%), copper(II) bromide (CuBr2, Sigma Aldrich, purity 99%), copper(I)
2.3. Example of the 2,6-DMP polymerization and the product extraction
bromide (CuBr, Sigma Aldrich, purity 98%), copper(II) carbonate basic
(CuCO3, Sigma Aldrich), copper(I) oxide (Cu2O, Sigma Aldrich, purity >
The polymerization was carried out at 25 ◦ C in a glass reactor
99%), toluene (Chempur, purity 99,5%), N,N-dibutyletylenediamine
equipped with a mechanical stirrer, thermostat, reflux condenser and a
(dbeda, Sigma Aldrich, purity ≥ 98%), N,N’-dimethylbutylamine
nozzle supplying molecular oxygen. To the solution of 0.159 g (0.79
(dmba, Sigma Aldrich, purity 99%), ethanol (Vevex, purity 99,8%)
mmol) 4-Br-2,6-DMF in the 71 ml of toluene and 1 ml of methanol, the
methanol (Chempur, purity ≥ 99%), ethylenediaminetetraacetic acid
0.035 g (0.109 mmol) of CuBr/dbeda catalyst and 0.16 g (1.58 mmol)
disodium salt (H4edta, POCh S.A., purity ≥ 99%), hydrochloric acid
dmba solution in 0.6 ml of toluene were added while stirring. Then
(HCl 35–38% wt., POCh S.A.) were used as received.
oxygen bubbling was started and after 10 min. a 50% solution of 2,6-
DMP (13.25 g, 0.108 mol) in toluene was dosed. After the process
2.2. Catalyst preparation (anhydrous and anaerobic conditions)
completion, the catalyst was deactivated with H4edta, and the polymer
was precipitated with methanol. The filtered off PPO was dissolved in
CuBr2/dbeda: 2 g (8.95 mmol) of CuBr2 was weighed, dissolved in
THF, reprecipitated and dried to constant weight.
75 ml methanol and heated until completely dissolved. The 1.76 ml
For the CuBr/dbeda catalytic system (the molar ratio of 2,6-DMP/Cu
dbeba solution in 5 ml methanol was then added dropwise to the solu­
= 1000, reaction time = 30 min.) polymerization was carried out using
tion for approx. 3 min. After the addition, the solution was boiled for one
the molar ratio of 4-Br-2,6-DMP/Cu = 8, 9, and 10, and the PPO with the
hour. The resulting, precipitated red crystalline product was filtered off
yield, respectively, 87.9%, 93.1% and 82.3% was obtained. The highest
while still being hot. After cooling, the product was washed with ether
PPO yield was obtained for 4-Br-2,6-DMP/Cu = 9 ratio and therefore
and dried under an oil pump vacuum at room temperature. A red
used for all experiments.
product was obtained with the yield of 89%. Elemental analysis showed
The PPO yield was calculated according to the Eq. (1):
(average) 30,32% C, 5,87% H and 7,08% N.
CuBr/dbeda: The acetonitrile used for the reaction was distilled Polymer, g
Yield, % = x 100
from P2O5, dbeda was distilled from BaO, whereas hexane - from Na/K Monomer, g
alloy. 7.15 g (49.84 mmol) CuBr was placed in the extraction chamber of
Repeatability of the polymerization was ± 5 wt%.
the Soxhlet extractor, while 12.9 g (74.86 mmol) of dbeda (50% in
excess) in 100 ml of acetonitrile was added to the flask. The extraction
was conducted in the reflex for 4 h. Subsequently, the flask contents was
cooled down in the ice-water bath and the precipitated white solid was

2
S. Firlik et al. Molecular Catalysis xxx (xxxx) xxx

Table 1 Table 4 presents the results of Mw, Mn and Đ measurements of

Yield and molar mass of PPO obtained in the presence of CuBr/dbeda system. samples taken from the run of the PPO synthesis.
Molar ratio 2,6- Reaction time, Yield, Mw, g/ Mn, g/ Đ A constant increase in the Mw (to 12 200 g/mol) and Mn (to 7600) as
DMP/Cu min. % mol mol well as Đ up to 1.6 was observed in the time range of 30÷60 min. From
1000 70 93.8 46 000 24 600 1.9 70 to 130 min., a steady increase in the Mw to 98 400 g/mol was
1000 100 99.9 59 000 29 000 2.0 identified, while the Mn value increases up to 49 100. The Đ value
1800 140 99.4 22 750 7 250 3.1 changed from 1.8 to 2.5 in the range of 70–130 min.

2.4. Method of testing 3.2. Catalytic Cu[II] systems

The molar mass (Mw, Mn) and dispersity index (Đ) of PPO were
measured by gel permeation chromatography (GPC) using an apparatus
of LabAlliance. The apparatus was equipped with a refractometric de­
tector and a Jordi Gel DVB Mixed Bed (250 mm × 10 mm) column. The
polystyrene was used as a standard calibration sample and chloroform as
a solvent.
The content of C, H and N was determined using the Elementar Vario
EL III CHNS analyzer. The accuracy of the marking was ± 0.3 wt.%.
3. Results and discussion
3.1. Catalytic Cu[I] systems
3.1.1. Polymerization catalyzed by CuBr/dbeda system
The results of polymerization of 2,6-DMP in the presence of CuBr/
dbeda and the characteristics of resulting polymers have been demon­
strated in Table 1.
After 70 min., when 2,6-DMP/Cu ratio is equal to 1000 and the re­
action yield already amounts to 93.8%, further extension of the reaction
time to 100 min results in a slight increase of efficiency however at the
same time the Mw increases from 45 000 g/mol to 59 000 g/mol, along
with a Đ. By increasing the 2,6-DMP/Cu ratio to 1800, the polymeri­
zation yield of 99.4% is obtained not sooner than after 140 min. and its
product is characterized by a significantly lowered Mw and Mn, while the
value of the Đ is relatively high, Đ = 3.1.
Table 2 exhibits the results of Mw, Mn and Đ measurements of sam­
ples taken from the run of the PPO synthesis.
According to the results presented in Table 2, the Mw values amount
to approx. 2500 g/mol, Mn = 1800 g/mol, Đ = 1.4 in the time up to 20
min. Over the next 50 min., the Mw, Mn increased, respectively to 12 700
and 7 900 g/mol. The Đ for that sample was 1.6. In the range of 60 to 70
min., a rapid increase in the molar mass from Mw 35 700 to 54 400 g/
mol and Mn 11 300 to 26 100 is observed with Đ value slightly above 2.
In the further reaction run, Mw gradually increased to 59 500 g/mol and
Mn up to 29 500 at the constant Đ = 2.
3.1.2. Polymerization catalyzed by Cu2O/Br2/dbeda system
The yield of PPO synthesis and the polymer characterization are
shown in Table 3.
The reaction yield depended on the 2,6-DMP/Cu ratio and poly­
merization time thus amounted 95.4% after 70 min., 99% after 140 min.
of the polymerization run at the 2,6-DMP/Cu = 1000. At the molar ratio
of 2,6-DMP/Cu = 1800 after 140 min. PPO with the yield of 93.4% was
obtained. As for the CuBr/dbeda system, shorter reaction time and
increased monomer/Cu ratio resulted in the lowered PPO molar mass.
The results obtained for the study of catalysts based on Cu[II] com­
plexes under Hay’s system operating conditions are presented in
Tables 5–8.
3.2.1. Polymerization catalyzed by CuBr2/dbeda system
The results of 2,6-DMP polymerization in the presence of CuBr2/
dbeda catalytic system are presented in the table 5.
The reactions carried out in the reaction times corresponding to the
ones involving catalyst systems with Cu[I] produced PPO with smilar
yields but lower molar mass. At the 2,6-DMP/Cu = 1000, resulting
PPO’s were characterized by significantly low Mw (up to 5 800 g/mol
after 140 min.) and Mn (ca. 3 000 g/mol).
When 2,6-DMP/Cu amounts to 1800, Mw = 7550 g/mol and Mn =
3500. However in this instance the increase in the monomer/Cu ratio
resulted in lower molar mass than it was the case in the systems con­
taining Cu[I] complexes. Dispersion coefficient values for the polymer
obtained after 70 min amounted to 1.6, whereas for the remaining
polymers ~ 2.
As previously, examinations of samples taken at different reaction
times were carried out, (Table 6).
After 70 min. of the reaction, Mw, Mn and Đ values for the sample
amounted to 3200 g/mol, 2200 and 1.4, respectively. After that time, a
slow increase of the molar mass was observed, with a constant Đ= 2. The
Mw value was increasing from 10 700 g/mol (130 min.) to 29 100 g/mol
(190 min). For Mn the increase amounted to 5 400 to 14 100 g/mol
respectively.
3.2.2. Polymerization catalyzed by CuCO3/Br2/dbeda system
CuCO3 can be found in nature as a mineral called malachite. Its
availability was a determining factor in using it as a component of the
catalyst system in the PPO synthesis [6]. The results of investigation of
this system are presented in the Tables 7 and 8.
The yields as well as Mw, Mn and Đ values of the reaction products
are presented in Table 7 and 8.
After 70 min. of polymerization, the PPO yield reached 99.4%. It
implies that this reaction system is the most active one in comparison to
other systems under investigation. On the other hand, Mw and Mn values
are relatively small and amount to 2700 and 2400 g/mol, respectively. It
is accompanied by a remarkably low Đ = 1.1.
Table 3
Yield and, molar mass of PPO obtained in the presence of Cu2O/Br2/dbeda
system.
Molar ratio 2,6-DMP/Cu Reaction time,
min. Yield,% Mw, g/mol Mn, g/mol Đ

Polymer was characterized by the lowest Đ after 70 min. of the reaction 1:1000 70 95.4 36 800 22 400 1.6
run. 1:1000 140 99.0 93 700 44 500 2.1
1:1800 140 93.4 15 150 6 850 2.2

Table 2
. Effect of polymerization time on PPO molar mass; molar ratio of 2,6-DMP/Cu = 900.
Reaction time, min. 10 20 30 40 50 60 70 100 130

Mw, g/mol 2 300 2 600 4 600 7 200 12 700 35 700 54 400 57 600 59 500
Mn, g/mol 1 800 1 800 2 400 4 500 7 900 16 200 26,100 28 600 29 500
Đ 1.3 1.4 1.9 1.6 1.6 2.2 2.1 2.0 2.0

3
S. Firlik et al. Molecular Catalysis xxx (xxxx) xxx

Table 4
Effect of polymerization time on PPO molar mass; molar ratio of 2,6-DMP/Cu = 900.
Reaction time, min. 30 50 60 70 80 90 100 110 120 130

Mw, g/mol 2 700 5 900 12 200 45 500 67 300 76 000 83 300 88 500 93 900 98 400
Mn, g/mol 2 000 3 600 7 600 18 100 29 800 34 100 47 300 48 200 44 900 49 100
Đ 1.4 1.6 1.6 2.5 2.3 2.2 1.8 1.8 2.1 2.0

Table 5 As demonstrated in Table 7 and 8, after 70 min. a complete con­

Yield and molar mass of the PPO obtained in the presence of CuBr2/dbeda version of monomer taken place and the molar mass of the PPO un­
system. changed until 180 min. of polymerization run. After that, the Mw and Mn
values of the PPO increased, while Đ slightly decreased.
Molar ratio 2,6- Reaction time, Yield, Mw, g/ Mn, g/ Đ
DMP/Cu min. % mol mol

1:1000 70 98.1 4 900 3 000 1.6

3.3. Mechanism proposal of the PPO synthesis
1:1000 140 99.8 5 800 2 900 2.0
1:1800 140 95.0 7 550 3 500 2.2
Catalytic systems involving Cu[I] and Cu[II] complexes with dbeda
ligands were added directly to the reaction mixture prior to 2,6-DMP
Table 6 addition and oxygen sparging. Whereas systems based on Cu2O/Br2
Effect of polymerization time on PPO molar mass; molar ratio of 2,6-DMP/Cu = and CuCO3/Br2 were used as a catalytic solution with 2,6-DMP in
1100*. CH3OH.
Reaction 70 130 140 150 160 170 180 190 The reaction of bromine with these copper compounds is rather
time, min. impossible, whereas the bromination of phenol with bromine constitutes
Mw, g/mol 3 10 14 16 20 23 25 29
a preparative reaction [18]. The postulated reactions taking place in the
200 700 000 500 400 300 300 100 obtained mixture are, as follows:
Mn, g/mol 2 5 7 8 10 12 12 14 Reaction of 2,6-DMP with bromine yields 4-Br-2,6-DMP and HBr,
200 400 400 400 000 100 800 700 reaction 1:
Đ 1.4 2.0 1.9 2.0 2.0 1.9 2.0 2.0
*
Additional source of bromine, 4-Br-2,6-DMP.

Table 7
Yield and molar mass of the PPO obtained in the presence of CuCO3/Br2/dbeda
Another preparative reaction of obtaining transition metal bromides
system.
is the reaction of their oxides, hydroxides and carbonates with HBr.
Molar ratio 2,6- Reaction time, Yield, Mw, g/ Mn, g/ Đ Thus, in the case under investigation, the resulting HBr is the reagent in
DMP/Cu min. % mol mol
the process of obtaining Cu[I] and Cu[II] bromides, reactions 2 and 3:
1000 70 99.4 2700 2400 1.1
1000 140 99.6 4400 3800 1.2 Cu2O + 2 HBr → 2 CuBr + H2O (2)
1800 140 93.8 5600 4150 1.3
CuCO3 + 2 HBr → CuBr2 + CO2 + H2O (3)

In this preparation step 4‑bromo-2,6 dimethylphenol, CuBr and

The extension of the reaction time does not contribute to the changes
in yield values, however Mw and Mn increased to 4400 and 3800 g/mol
and the Đ to 1.2. The increase of monomer/Cu ratio to 1800 entailed, as
in the case of CuBr2/dbeda system, higher values of molar mass.
Table 8 exhibits the results of Mw, Mn and Đ measurements of sam­
ples taken from the run of the PPO synthesis.
CuBr2 are obtained, respectively. At that moment, 4-Br-2,6-DMP be­
comes the source of bromine, similarly as in the case of CuBr/dbeda and
CuBr2/dbeda systems.
The polymerization of 2,6-DMP to PPO is running according to the
following reaction 4:

Table 8
Effect of polymerization time on PPO molar mass; molar ratio of 2,6-DMP/Cu = 1000.
Reaction time, min. 80 100 110 130 140 150 170 180 210 240

Mw, g/mol 2 700 2 100 2 200 1 900 2 000 2 400 2 200 4 400 5 000 6 000
Mn, g/mol 1 400 1 500 1 600 1 400 1 400 1 500 1 600 3 800 4 200 4 700
Đ 1.9 1.4 1.4 1.4 1.4 1.6 1.4 1.2 1.2 1.3

4
S. Firlik et al.
Scheme 3. Activation step of 2,6-DMP polymerization by Cu[I] complex.
This is a typical reaction, where the formation of thermodynamically
stable water molecules shifts its equilibrium towards the products. This
polymerization runs in Cu[I]/Cu[II] catalytic system, where the copper
ions are complexed with a chelate ligand, i.e. dbeda.
In these systems, as reported previously, the Cu[I] ions are more
stable due to their electronic configuration of 3 d10, and that of Cu[II] -
3d9. Thus, the transition from the Cu[II] ion to the Cu[I] ion will be
favored, while the transition of Cu[I] to the Cu[II] ion will require
additional energy. It is relatively low and amounts to ~ 15 eV. The Cu
[II] ions will therefore "seek" the source of one electron to become
converted into Cu[I] ion.
Such a process is taking place when Cu[II] ions react with phenols [8,
11]. The interaction of this ion with the hydroxyl group of phenol leads
to a homolytic cleavage of the OH group into the phenoxy radical and
the hydrogen radical, which in turn, results in HBr and Cu[I] in a ho­
molytic reaction with Cu[II]-Br bond, scheme 3:
The Cu[II]-Br bond therefore constitutes the source of the electron.
In turn, stable Cu[I] ion reacts with organic halides in complexes with
chelated organic ligands in the ATRP process to form carbon radicals
and Cu[II] complexes [5].
Apparently, it should be assumed that phenoxy radical formation
reactions will run more efficiently than carbon radical formation
reactions.
As mentioned previously, the 9-fold excess of 4-Br-2,6-DMP in rela­
tion to Cu is taking place in the catalytic mixture at the initial stage of
the process. That excess is encountered by copper[I] or copper[II]
complexes depending on the catalyst used, prior to starting 2,6-DMP
addition and oxygen sparging, respectively.
The individual transformations of Cu complexes and the reaction
products are presented in the scheme 4:
In the first step, the Cu[I] complexes in the reaction with 4-Br-2,6-
DMP are transformed into Cu[II] complexes and produce para carbon
Scheme 4. Comparison of activation step induced by Cu[I] and Cu[II] catalyst.
5
Molecular Catalysis xxx (xxxx) xxx
Scheme 5. PPO oligomer formation.
radicals. In turn, Cu[II] complexes in the reaction with the bromine
derivative are transformed into Cu[I] complexes and produce oxygen
located radicals and HBr. Next, obtained radicals undergo trans­
formations leading to diradicals formation.
Taking into consideration the greater stability of the Cu[I] ion, the
reactions involving Cu[II] are favored and yield higher concentration of
Cu[I] complexes at the process beginning Consequently, it will cause a
greater number of polymerization catalysts when using Cu[II] com­
plexes. Those reactions run until 4-Br-2,6-DMP is completely converted.
The resulting diradicals can react with each other to form oligomers
still appearing as diradicals containing up to 9 aromatic rings when the
mono diradicals have run out i.e. the amount of excess of 4-Br-2,6-DMP
in the initial reaction mixture, scheme 5.
At the end of this step the final products are HBr molecules, 2,6-DMP
and carbon-oxygen diradical containing 9 aromatic rings as well as Cu[I]
and Cu[II] complexes.
Oxygen is supplied to a such system and 2,6-DMP addition is started
dropwise. The introduction of oxygen will launch the following process.
The reactions of oxygen with hydrogen halides to produce water and
molecules of a given halogen are well known. Thus, the following re­
action should occur in the investigated case [19,20]:
4 HBr + O2 → 2 Br2 + 2H2O (5)
At that point, 9 HBr molecules appear in the investigated system. For
this amount, the stoichiometric reaction of HBr with oxygen is, as fol­
lows - reaction 6:
18 HBr + 4.5 O2 → 9 H2O + 9 Br2 (6)
The resulting bromine molecules will constitute a kind of “bromine
stock”, scheme 6.
The Br2 molecule will be used for the bromination of the stepwise
added 2,6-DMP. This will reduce the bromine resources in the system
from 4.5 Br2 to 3.5 Br2.
In this radical reaction, one bromine atom forms a C-Br bond in the 4-
Br-2,6-DMP, whereas the other atom forms the bond in the HBr
molecule.
S. Firlik et al.
Scheme 6. Detailed mechanism of 2,6-DMP polymerization to PPO.
CuBr/dbeda complex is responsible for the conversion of 4-Br-2,6-
DMP into the para-carbon 2,6-DMP radical and CuBr2/dbeda forma­
tion. In this reaction homolytic cleavage of C-Br bond in 4-Br-2,6-DMP
occurs. The "migration” of the bromine atom to the Cu[II] complex
constitutes the first step of the 2,6-DMP polymerization.
The second stage running parallel is the 2,6-dimethylphenoxy radical
formation as the result of the 2,6-DMP reaction with the Cu[II]complex.
Products of this reaction include the Cu[I] complex and HBr. It means
that the bromine atom is now found in that hydrogen bromide. This
process can be called the "Cu[I]/Cu[II] cycle".
This hydrogen bromide and the one originating from the 2,6-DMP
bromination process with oxygen-reaction 5 produce water and Br2
which will supplement back the “bromine stock” to 4.5 Br2 - the
“bromine cycle”.
The formed in this step oxygen and carbon radicals will react with
the actual 9-ring diradical to its alpha hydroxy omega-phenyl derivative,
i.e. already 12-ring diradical. Thus, this new derivative is equipped with
an OH group capable of forming an oxygen radical, while a phenyl ring
is ready to form a carbon radical via bromination and reaction with a Cu
[I] complex. The resulting new diradicals will propagate the PPO chain
as demonstrated in scheme 5.
In the next cycle, PPO diphenyl monomer will be already formed,
6
Molecular Catalysis xxx (xxxx) xxx
terminated with OH group and a phenyl ring and ready to be converted
into diradicals, as discussed above.
2,6-DMP polymerization reminds the living polymerization mecha­
nism. PPO oligomer characterized with the relatively low molar mass
and Đ ~ 1.5 are formed at the very beginning of polymerization.
It is known that the higher the Đ, the greater the mass dispersion.
When Đ = 1, the molar mass of polymer molecules remains the same,
however, it never takes place in the case of synthetic polymers. The
smallest Đ is achieved in the living polymerization.
For the vast majority of industrial synthetic polymers Đ is 1.5 − 2.
This indicate that the polymerization proceeded in conventional
manner. The Đ > 2 indicates unusual or excessive polymerization dis­
turbances that must be eliminated.
While the reaction continues, obtained oligomers and respectively
longer chains with alpha hydrodroxy and omega phenyl substituents are
combined with spike-growing PPO chains of correspondingly high molar
mass and Đ ~ 2. In investigated cases, this process is terminated with the
addition of H4edta.
In our study at 2,6-DMP/Cu ratio = 1000, when the polymerization
yield amounted ~ 99%, approx. 1 mol% of PPO chains contains nine
phenyl units derived from 4-Br-2,6-DMP-based diradicals (scheme 5 step
I) and 99% of the phenyl dimer units formed in the step II.
S. Firlik et al.
The increases of PPO chain length depends on the used catalytic
system. At the 2,6-DMP/Cu ratio = 1000 when Cu[II] complex is
applied, 2,6-DMP is relatively quickly almost converted completely and
the obtained PPO is characterized by a relatively lower molar mass in
comparison to the polymer obtained with Cu[I] catalyst. For higher ratio
of 2,6-DMP/Cu = 1800, the Cu[II] catalyst gives PPO characterized by
relatively higher molar mass than the Cu[I] catalyst, table 1-8. This
scheme is characteristic for two systems having different numbers of
active centers at the same monomer amount.
At the higher number of the active catalyst centers and the constant
number of monomer molecules there is less molecules per the active
catalyst site. Thus, at 99% monomer conversion PPO will be charac­
terized by lower molar mass than the polymer obtained at the lower
number of the catalyst center and the constant monomer amount.
When the 2,6-DMP/Cu ratio is 1800, PPO with much lower molar
mass was obtained by Cu[I] catalysts, than it was the at 2,6-DMP/Cu =
1000. The reverse effect was observed for Cu[II] catalysts. Fewer poly­
merization centers in the first case means PPO oligomers were formed
for a relatively long period of time. Thereby, more polymerization
centers shortens oligomer formation time and low-molecular oligomers
sooner polymerize to high-molecular PPO.
The greater number of catalytic centers for Cu[II] system results from
a thermodynamically more favorable Cu[II] → Cu[I] reaction than the
Cu[I] → Cu[II] reaction [1].
4. Conclusions
The study of catalytic activity of the systems containing Cu[I] com­
plexes (CuBr/dbeda, Cu2O/Br2/dbeda) and Cu[II] complexes (CuBr2/
dbeda, CuCO3/Br2/dbeda) demonstrated a higher number of polymeri­
zation centers formed for Cu[II] catalysts in the PPO synthesis, where
the ratio Br/Cu = 9. The molar mass and its distribution depended on
2,6-DMP/Cu ratio and the polymerization time. For the molar ratio of
2,6-DMP/Cu = 1000, PPO with higher molar mass was obtained by the
Cu[I] catalysts. When the 2,6-DMP/Cu ratio increased to 1800, the PPO
molar mass decrease was observed, however the reverse effect was
observed for the Cu[II] system.
In the presence of the used catalysts, 2,6-DMP to PPO polymerization
mechanism was proposed and the role of the bromine excess in the re­
action was presented. In the proposed mechanism the Cu[I]/Cu[II]
systems is responsible for the formation of oxygen and carbon radicals
which launch the PPO formation.
The "bromine system” reversibly provides the bromine molecule for
4-Br-2,6-DMP formation. The resulting molecule in the reaction with Cu
[I] complex provides a para-carbon radical.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
The research was performed at Industrial Chemistry Research Insti­
tute (currently Łukasiewicz - Industrial Chemistry Research Institute)
within the research project “Complex Technology for Production of
Engineering Polymers Based on Poly(phenylene oxide)”, realized within
The Operational Programme Innovative Economy (2009–2013), project
No WND-POIG.01.03.01–14–058.
Molecular Catalysis xxx (xxxx) xxx
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