Self-immobilized catalysts for ethylene polymerization based on various phenoxyimine titanium halide complexes

Article abstract of DOI:10.1007/s11172-012-0116-4

The kinetic features of ethylene polymerization on ten methylalumoxane- activated self-immobilized bis(phenoxyimine) complexes of titanium chloride of various structure containing oxyallyl functional groups were studied. The catalytic activity of the syst

Full text of DOI:10.1007/s11172-012-0116-4

Russian Chemical Bulletin, International Edition, Vol. 61, No. 4, pp. 836—842, April, 2012
836
Selfꢀimmobilized catalysts for ethylene polymerization based on various
phenoxyimine titanium halide complexes
N. I. Ivancheva,a D. V. Sanieva,a S. P. Fedorov,a I. V. Oleinik,b I. I. Oleinik,b G. A. Tolstikov,b and S. S. Ivancheva
aG. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Saint Petersburg Department,
14 prosp. Dobrolyubova, 197198 Saint Petersburg, Russian Federation.
Fax: +7 (812) 323 0557. Eꢀmail: ivanchev@SM2270.spb.edu
bN. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
9 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9524. Eꢀmail: oleynik@nioch.nsc.ru
The kinetic features of ethylene polymerization on ten methylalumoxaneꢀactivated selfꢀ
immobilized bis(phenoxyimine) complexes of titanium chloride of various structure containing
oxyallyl functional groups were studied. The catalytic activity of the systems was determined in
the temperature range 20—60 С under ethylene pressure 0.4 MPa. The positions and structures
of the oxyallyl group and substituents in the phenoxy groups of the complexes substantially
change the activity of the catalytic systems based on these complexes, the rate of the selfꢀ
immobilization of the catalysts on the polymer, and molecular weights and molecular weight
distributions of the obtained polyethylenes.
Key words: bis(phenoxyimine) titanium halide complexes, oxyallyl groups, homogeneous
and heterogeneous catalysis, polymerization, selfꢀimmobilization, polyethylene.
Selfꢀimmobilization of catalysts with a certain strucꢀ
ture directly in the course of polymerization is a new conꢀ
cept of the formation of supported catalysts during ethylꢀ
ene or ꢀolefin polymerization. The concept is based on
the possibility of catalyst incorporation into the formed
polymer due to the functional group in the catalyst strucꢀ
ture, which is capable of copolymerizing with the polyꢀ
merized olefin.
The concept of selfꢀimmobilization was advanced and
substantiated in several studies of metallocene cataꢀ
lysts for ethylene polymerization functionalized by vinyl,
ꢀalkynyl, or alkyne groups,1—10 and in studying of ethylꢀ
ene polymerization catalyzed by the functionalized bisꢀ
(imino)pyridine iron complexes activated by methylaluꢀ
moxane (MAO).11
catalytic complex were determined. The study of the IR specꢀ
tra of the obtained polymers made it possible to detect the
characteristic band (1258 cm–1), intensity of which increasꢀ
es with an increase in the rate of immobilization of the
catalytic system during polymerization. Thus, the assumpꢀ
tion about the possible incorporation of the catalyst into
the polyethylene formed was experimentally confirmed.17
The results of studying the catalytic polymerization of
ethylene are described in the present article. Specially synꢀ
thesized MAOꢀactivated functionalized bis(phenoxyimꢀ
ine) titanium halide complexes were used as catalysts. It
was of interest to reveal a relationship between the strucꢀ
ture of the catalytic system and the kinetics of selfꢀimmoꢀ
bilized polymerization and characteristics of obtained PE.
This concept was further developed when studying selfꢀ
immobilization during ethylene polymerization on the
neutral oneꢀcomponent phenylnickel(II) salicylaldiminꢀ
ates functionalized by oxyallyl groups12—14 and the cataꢀ
lysts based on the Ti or Zr halide 4ꢀphenoxyimine comꢀ
plexes functionalized by oxyallyl groups.15
We studied specific features of the selfꢀimmobilization of
catalysts based on the titanium bis(phenoxyimine) complexꢀ
es of different structures modified by oxyallyl groups and acꢀ
tivated by MAO during ethylene polymerization.16—18 The
immobilized active polymer catalysts formed on the surface
of obtained polyethylene (PE) were isolated, and the deꢀ
pendences of their activity on the structure of the initial
Results and Discussion
The catalytic activity in ethylene polymerization was
studied in the presence of bis(phenoxyimine) titanium
chloride complexes 1—10 with functional oxyallyl groups
in the paraꢀ (1—6) and metaꢀpositions (7—10) of the pheꢀ
nyl ring at the imine nitrogen atom and with alkylaryl
substituents in the phenoxy groups.
The bis(phenoxyimine) ligands for the titanium dichlorꢀ
ide complexes were synthesized by the reactions of
3ꢀcumylꢀ or 3,5ꢀdicumylꢀsubstituted aldehydes with pꢀallylꢀ
oxyaniline (n = 1), pꢀ[(butꢀ3ꢀenyl)oxy]aniline (n = 2),
and pꢀ[(pentꢀ3ꢀenyl)oxy]aniline (n = 3) hydrochlorides
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0833—0839, April, 2012.
1066ꢀ5285/12/6104ꢀ0836 © 2012 Springer Science+Business Media, Inc.

Selfꢀimmobilized catalysts for polymerization
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
837
R1
R2
n
R1
R2
H
n
R1
R2
n
R1
R2
n
R1
CMe2(Ph) CMe2(Ph)
10 CMe2(Ph) CMe2(Ph)
R2
n
1
2
CMe2(Ph)
CMe2(Ph)
H
H
1
2
3
4
CMe2(Ph)
CMe2(Ph) CMe2(Ph)
3
1
5
6
CMe2(Ph) CMe2(Ph)
CMe2(Ph) CMe2(Ph)
2
3
7
8
CMe2(Ph)
CMe2(Ph)
H
H
1
2
9
1
2
Scheme 2
or with similar metaꢀanilines (n = 1, 2) on reflux in methꢀ
anol in the presence of triethylamine (Scheme 1). The
yields were 87—89%.
Scheme 1
Ti—N bonds, at 524—566 cm–1 corresponding to vibraꢀ
tions of the Ti—O bonds, and at 1596—1610 cm–1 caused
by vibrations of the N=CH bonds. The 1Н NMR spectra
exhibit the signals of protons of the НС=N groups at 
7.57—7.95 along with signals of the aromatic protons, the
methyl groups of the cumyl substituent, and the alkenyꢀ
loxy group; the singlets of the OH groups observed in imiꢀ
nes are absent.
The results of studying the kinetic features of ethylꢀ
ene polymerization at 20, 40, and 60 С on complexes 1—10
are presented in Table 1.
R1, R2 = H, CMe2(Ph); n = 1—3
The oneꢀpot method of the reaction of the ligand with
TiCl2(OPri)2 in a toluene solution at ambient temperature
was used for the synthesis of the complexes.17,18 The
titanium(IV) dichloride complexes were synthesized in high
yields (Scheme 2).
The compositions and structures of the synthesized
ligands and titanium complexes 1—10 with the correꢀ
sponding structures were confirmed by the analytical and
spectral data.
The catalytic activity and molecular weights (MW) of
the formed PE depend on the structural specific features
of the complexes formed: the character and positions of the
substituents in the phenoxy groups, the number of СН2
groups in the oxyallyl functional group, and its position.
An analysis of the data presented in Table 1 shows that
the highest activity is observed for systems 1 and 6, and it
depends weakly on the polymerization temperature. The
intrinsic viscosity () or equivalent MW of the PE formed
(M) increases with temperature. However, for catalytic
The IR spectra of the complexes contain absorption
bands at 437—478 cm–1 corresponding to vibrations of the

838
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Ivancheva et al.
Table 1. Results of ethylene polymerization on MAOꢀactivated functionalized bis(phenoxyimine) complexes of titanium dichlorꢀ
ide 1—10a (Tpol is the polymerization temperature, А is activity, M is the molecular weight corresponding to the intrinsic viscosity ,
and Cr is crystallinity)
Complex n Tpol
/C
[Ti]
/mol
Yield
/g
Ab
M•10–6 0.5
/g mol–1
DSC
M.p./C H/J g–1 Cr (%) CH3/1000 C CH=CH2/1000 C
IRc
1
1
1
1
2
2
2
3
3
3
1
1
1
2
2
2
3
3
3
1
1
1
2
2
2
1
1
1
2
2
2
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
20
40
60
0.523
0.58
0.47
0.7
0.7
0.7
0.546
0.55
0.6
0.68
0.70
0.721
0.623
0.670
0.623
0.48
0.44
0.48
0.698
0.640
0.640
0.50
0.50
0.50
0.50
0.55
0.456
0.89
1.29
0.98
6.041 29.0
7.861 34.0
5.883 31.0
4.109 14.7
4.410 15.8
3.206 11.5
4.513 20.7
4.673 21.2
3.033 12.6
6.914 25.4
7.191 25.7
2.8
6.0
8.7
1.5
2.5
2.3
1.1
2.0
3.5
02.87
03.13
5.8
2.6
4.0
3.8
01.05
2.4
2.6
4.3
4.2
2.7
1.8
2.7
4.3
4.4
3.5
1.7
1.7
3.5
4.8
141.7
143.9
144.1
141.2
140.6
141.7
140.1
140.8
141.6
141.4
141.8
141.5
141.6
141.1
139.9
140.9
142.6
142.4
142.2
142.7
141.6
142.7
141.2
140.9
141.8
141.5
139.1
140.3
142.3
142.7
221
226
228
225
231
232
214
216
212
261
252
244
225
245
255
217
220
222
226
226
237
234
237
249
240
234
243
237
237
246
76
77
78
77
79
79
73
74
75
89
86
83
77
84
87
74
75
76
77
77
81
80
81
85
82
80
83
81
81
84
0
0
0
0.05
0.04
0.03
0.10
0.11
0.10
0.06
0.10
0.07
0.03
0.02
0.02
0.05
0.05
0.05
0.05
0.05
0.03
0.065
0.08
0.105
0.04
0.05
0.04
0.03
0.05
0.07
0.06
0.05
0.03
2
0.15
0.05
0.05
0
0.1
0.05
0.35
0
0
0
0.05
0
0
0
0
0.05
0.05
0.1
0
0
0
0
0
3
4
5.25
18.2
5
6.835 27.4
5.568 20.8
4.073 16.3
6
8.1
9.0
8.95
42.0
51.0
47.0
7
4.785 17.1
8.334 32.6
5.438 21.2
6.462 32.3
4.632 23.2
2.177 10.9
3.313 16.8
5.720 26.0
5.274 28.9
3.931 11.0
8.897 17.2
4.537 11.6
8
9
0
10
0.05
0.05
0.05
a Polymerization conditions: 50 mL of toluene, ethylene pressure 0.4 MPa, MAO : Ti = 500 : 1 (mol mol–1),  = 1 h.
b In (kg of PE) (mmole of complex)–1 MPa–1 h–1
.
c The number of terminal methyl and vinyl groups (per 1000 C atoms) measured by the characteristic bands at 1378 and 909 cm–1
respectively.
,
system 1 the value of M changes ~4ꢀfold (from 2.8•106
to 8.7•106 g mol–1), whereas for system 6 the change is
only ~1.5 times (from 1.05•106 to 2.6•106 g mol–1). In
systems 6 and 1, the oxyallyl group is in the paraꢀposition,
but system 6 differs from 1 by the presence of the
—(СН2)3— bridge in the oxyallyl group and substituent
CMe2Ph in the paraꢀposition of the phenoxy group.
The transition of the oxyallyl group in the complex of
the catalytic system in the metaꢀposition decreases, as
a whole, the activity of the systems; however, the influꢀ
ence of methylene bridges introduced into the oxyallyl
group changes. The activity is somewhat higher with the
elongation of the bridge, but the MW of PE decreases.
Thus, the activity of the studied catalytic systems varies
which makes it possible to obtain ultrahighꢀmolecularꢀ
weight polyethylene (UHMWPE).
The PE obtained are characterized by high crystalliniꢀ
ty (75—85%) and a low number of terminal methyl and
vinyl groups, which indicates an insignificant contribuꢀ
tion of chain transfer reactions to the monomer and MAO.
The influence of substituents in the phenoxy group on
the activity of catalytic systems is optimum in combinaꢀ
tion of substituent CMe2Ph in the orthoꢀposition and the
H atom in the paraꢀposition. The introduction of the oxyꢀ
allyl group into the paraꢀposition of the phenyl ring at the
imine nitrogen atom provides a high activity, which slightly
decreases upon the introduction of oxyallyl into the metaꢀ
position. No polymer is formed upon the addition of the
oxyallyl group into the orthoꢀposition. The optimum comꢀ
from 11 to 51 (kg of PE) (mmole of complex)–1 MPa–1 h–1
,

Selfꢀimmobilized catalysts for polymerization
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
839
W•10–3/kg (mole of complex)–1 min–1
W•10–3/kg (mole of complex)–1 min–1
0.8
0.8
0.7
0.6
0.5
0.6
2
0.4
0.4
0.2
1
0.3
0.2
0.1
1
3
3
2
10
20
30
40
50
60 /min
10
20
30
40
50
60 /min
Fig. 2. Kinetic curves of ethylene polymerization in the presence
of complex 1 at 20 (1), 40 (2), and 60 C (3).
Fig. 1. Kinetic curves of ethylene polymerization at 40 С in the
presence of phenoxyimine complexes 1—3 (W is the polymerꢀ
ization rate).
W•10–3/kg (mole of complex)–1 min–1
0.5
2
bination of activity and MW is achieved at the methylene
bridge length equal to 1. At n = 2 the activity decreases,
and at n = 3 the activity increases again but without an
increase in the MW of PE.
0.4
1
0.3
Let us consider the results characterizing the occurꢀ
rence of selfꢀimmobilization during polymerization. The
shape of the curves of ethylene uptake (Fig. 1) shows that
the initial high rate of homogeneous polymerization deꢀ
creases with time and transforms into the regime characꢀ
terized by a constant but lower rate of heterogeneous polyꢀ
merization. At this step of polymerization, the catalytic
system is almost completely immobilized on the polymer
formed.
0.2
0.1
3
10
20
30
40
50
60 /min
Fig. 3. Kinetic curves of ethylene polymerization in the presence
of complex 3 at 20 (1), 40 (2), and 60 C (3).
Selfꢀimmobilization begins from the first minutes for
catalytic system 1 (n = 1), and to the 20th minute the
catalyst is immobilized on the polymer formed and the
rate becomes constant. For system 2 (n = 2), the process
rate is the lowest and immobilization is completed within
20 min. For system 3 (n = 3), selfꢀimmobilization lasts
to 35 min.
lysts also suggests the "living" mechanism of polymerizaꢀ
tion and formation of macromolecules.
Complex 11 was used as a polymerization catalyst for
studying the MWD curves.
The curves of ethylene uptake rate vs. the time of polyꢀ
merization in the presence of complexes 1 and 3 at difꢀ
ferent temperatures are shown in Figs 2 and 3, respecꢀ
tively.
The curves characterize the overall occurrence of
two polymerization processes in a homogeneous system
in which the polymerization starts. As the reaction
proceeds, the catalyst gradually transforms into the
immobilized state and the process rate decreases. As
a result, the homogeneous component of polymerizaꢀ
tion disappears. The shape of these curves makes it
possible to estimate the selfꢀimmobilization rate of
each catalytic system. The reaction temperature can afꢀ
fect the selfꢀimmobilization rate and, as a consequence,
the rate of transition of the catalyst to the immobiꢀ
lized state.
The differential MWD curves of the PE samples obꢀ
tained in the presence of the studied systems at different
durations and conditions of polymerization are compared
in Figs 4 and 5.
The change in the differential curves of molecular
weight distribution (MWD) against time for various cataꢀ

840
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Ivancheva et al.
dwf/dlogM
molecules towards an increase in the HM fraction with
time (see Fig. 5).
Mp = 1027756
Mp = 772986
Mp = 291501
8.0
6.0
4.0
2.0
0
To compare specific features of macromolecular forꢀ
mation in simple nonꢀselfꢀimmobilized systems, we reꢀ
corded the MWD curves of the PE obtained on catalytic
system 12 similar in structure to complex 11 but without
oxyallyl groups (Fig. 6).
3
2 
1
1´
3
2´
1
2
3´
4.5
5.0
5.5
6.0
6.5
logM
Fig. 4. Differential curves of the MWD of PE obtained in the
presence of complex 11 at 20 С, 0.15 MPa, and polymerization
time 2 (1), 10 (2), and 15 min (3). The values of polydispersion
(Mw/Mn) are 3.66 (1), 3.47 (2), and 3.14 (3). The lowꢀ and highꢀ
molecularꢀweight fractions obtained by the separation of curves
1—3 are designated by 1´—3´ and 1—3, respectively. Here and
in Figs 5 and 6, Mw, Mn, Mp, and M are the average weight,
average numerical, peak, and average viscosity molecular weights,
respectively.
dwf/dlogM
A comparison of the polymerization kinetics on these
two catalytic systems indicates that the MW of the formed
PE increases much more slowly in the presence of comꢀ
plex 12 without the oxyallyl group than in the presence of
complex 11. For example, for the system without the oxyꢀ
allyl group the peak values of MW (Мp) detected in 10 min
are 3.23•105 g mol–1, whereas for complex 11 this value is
7.73•105 g mol–1. This fact, along with the symmetrical
unimodal shape of the MWD curve for the corresponding
sample of PE (see Fig. 6), indicates the absence of the
"living" mechanism of macromolecule formation in the
presence of the catalytic system, structure of which conꢀ
tains no functional groups capable to copolymerization.
Mp = 576332
Mp = 289376
Mw = 848784
8.0
6.0
4.0
2.0
0
Mw = 584898
Mp = 811236
1
2
3
Mw = 1070705
4.5
5.0
5.5
6.0
6.5
logM
Fig. 5. Differential curves of the MWD of PE obtained in the
presence of complex 11 at 40 С, 0.15 MPa, and polymerization
time 2 (1), 5 (2), and 10 min (3). The values of polydispersion
(Mw/Mn) are 3.27 (1), 2.6 (2), and 3.04 (3).
M = 340350
dwf/dlogM
Mp = 322455
0.8
As can be seen from the data in Figs 4 and 5, the MW
of the PE formed rapidly increases with time (Mw increasꢀ
es by ~20% within 3 min and by 45% within 8 min), which
is not characteristic of ethylene polymerization on simple
homogeneous catalytic systems.16 The division of the
MWD curves into the lowꢀmolecularꢀweight (LM) and
highꢀmolecularꢀweight (HM) fractions is shown in Fig. 4.
The change in the ratio of the surface areas restricted
by curves 1´—3´ and 1—3 indicates that a portion of
the LM fractions decreases with time and that of the
HM fractions increases. The average values of MW for the
HM fractions also increase with time, which is indicatꢀ
ed by the shift of maxima of the corresponding peaks toꢀ
wards an increase in MW. At 40 С the redistribution of
0.6
Mn = 167369
0.4
Mw = 471884
0.2
0
4.5
5.0
5.5
6.0
6.5
logM
Fig. 6. Differential curve of the MWD of PE obtained in the
presence of complex 12 at 25 С, 0.113 MPa, and polymerizaꢀ
tion time 10 min.

Selfꢀimmobilized catalysts for polymerization
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
841
(CDCl3), : 1.69—1.89 (m, 12 Н, СН3); 4.33—4.54 (m, 4 H,
ОСН2—СН=СН2); 5.20—5.42 (m, 4 H, ОСН2—СН=СН2);
5.95—6.08 (m, 2 H, ОСН2—СН=СН2); 6.43—7.63 (m, 24 H,
Н arom.); 7.76—7.82 (m, 2 H, СH=N). Found (%): С, 69.55;
H, 5.80; Cl, 8.09; N, 3.12. C50H48Cl2N2O4Ti. Calculated (%):
С, 69.85; H, 5.63; Cl, 8.25; N, 3.26.
Bis{2ꢀ{[4ꢀ(butꢀ3ꢀenyl)oxyphenylimino]methyl}ꢀ6ꢀ(ꢀcumyl)ꢀ
phenoxy}titanium(IV) dichloride (2). The yield was 94%. IR (KBr),
/cm –1: 1609 (C=N), 558 (Ti—O), 442 (Ti—N). 1Н NMR
(CDCl3), : 1.75—1.79 (m, 12 Н, СН3); 2.51—2.59 (m, 4 H,
ОСН2—CH2—СН=СН2); 3.94—4.03 (m, 4 H, ОСН2—CH2—
СН=СН2); 5.11—5.22 (m, 4 H, ОСН2—CH2—СН=СН2);
5.83—5.97 (m, 2 H, ОСН2—CH2—СН=СН2); 6.79—7.56
(m, 24 H, H arom.); 7.70—7.75 (m, 2 H, СH=N). Found (%):
С, 70.36; H, 5.86; Cl, 7.89; N, 3.11. C52H52Cl2N2O4Ti. Calcuꢀ
lated (%): С, 70.35; H, 5.90; Cl, 7.99; N, 3.16.
Bis{2ꢀ{[4ꢀ(pentꢀ4ꢀenyloxy)phenylimino]methyl}ꢀ6ꢀ(ꢀcumꢀ
yl)phenoxy}titanium(IV) dichloride (3). The yield was 95%. IR
(KBr), /cm–1: 1609 (C=N), 563 (Ti—O), 443 (Ti—N).
1Н NMR (CDCl3), : 1.42—1.52 (m, 12 Н, CH3); 1.81—1.93
(m, 4 Н, ОСН2—СН2—СН2—СН=СН2); 2.19—2.28 (m, 4 Н,
ОСН2—СН2—СН2—СН=СН2); 3.79—3.99 (m, 4 Н, ОСН2—
СН2—СН2—СН=СН2); 4.98—5.11 (m, 4 Н, ОСН2—СН2—
СН2—СН=СН2); 5.80—5.93 (m, 2 Н, ОСН2—СН2—СН2—
СН=СН2); 6.42—7.62 (m, 24 H, Н arom.); 7.82—7.95 (m, 2 Н,
СH=N). Found (%): С, 70.93; H, 6.12; Cl, 7.52; N, 3.11.
C54H56Cl2N2O4Ti. Calculated (%): С, 70.82; H, 6.16; Cl, 7.74;
N, 3.06.
Thus, we showed that a selfꢀimmobilizing of catalyst
on the formed polyethylene occurs in the course of polyꢀ
merization when catalytic systems based on the titaꢀ
nium halide bis(phenoxyimine) complexes of various strucꢀ
tures functionalized by oxyallyl groups are used as cataꢀ
lysts for ethylene polymerization. The activity and selfꢀ
immobilizing capacity of the catalytic systems depend subꢀ
stantially on the structures of substituents in the phenoxy
groups and the number of methylene units in the oxyallyl
group of the complex. When the catalytic systems with
active selfꢀimmobilization are used, UHMWPE with imꢀ
proved morphology is formed and the polymer does not
stick to the reactor walls during polymerization.
The data obtained allow a rational choice of catalytic
systems when obtaining UHMWPE.
Experimental
Ethylene was subjected to additional purification by passing
through columns packed with alumina; the ethylene content was
at least 99.9%, dew point –45 to –60 С. Argon ("extra") was
additionally purified from moisture traces by passing through
columns packed with calcined alumina. After purification the
dew point did not exceed –60 С. Polymethylalumoxane (Aldꢀ
rich) was used as a 10% solution in toluene. Toluene (analytical
purity grade) was doubly dried with freshly calcined alumina and
used as freshly distilled over metallic sodium in argon. Isopropyl
alcohol (special purity grade) was used as received. The viscosity
of polymer solutions was measured in a capillary Ubellohde visꢀ
cosimeter in decalin at 135 С. The average viscosity molecular
weight of the polymers (M) was calculated from the intrinsic
Bis{2ꢀ[(4ꢀallyloxyphenylimino)methyl]ꢀ4,6ꢀdi(ꢀcumyl)phenꢀ
oxy}titanium(IV) dichloride (4). The yield was 95%. IR (KBr),
1
/cm–1: 1609 (C=N), 553 (Ti—O), 466 (Ti—N). Н (CDCl3),
: 1.62—1.81 (m, 24 Н, СН3); 4.36—4.53 (m, 4 H, ОСН2—
СН=СН2); 5.19—5.42 (m, 4 H, ОСН2—СН=СН2); 5.89—6.06
(m, 2 H, ОСН2—СН=СН2); 6.38—7.54 (m, 32 H, Н arom.);
7.72—7.78 (m, 2 H, СH=N). Found (%): С, 74.41; H, 6.21;
Cl, 6.26; N, 2.68. C68H68Cl2N2O4Ti. Calculated (%): С, 74.52;
H, 6.25; Cl, 6.47; N, 2.88.
Bis{2ꢀ{[4ꢀ(butꢀ3ꢀenyl)oxyphenylimino]methyl}ꢀ4,6ꢀdiꢀ
(ꢀcumyl)phenoxy}titanium(IV) dichloride (5). The yield was 87%.
IR (KBr), /cm–1: 1609 (C=N), 558 (Ti—O), 466 (Ti—N).
1Н NMR (CDCl3), : 1.68—1.78 (m, 24 Н, СН3); 2.48—2.59
(m, 4 H, ОСН2—CH2—СН=СН2); 3.97—4.05 (m, 4 H,
ОСН2—CH2—СН=СН2); 5.13—5.22 (m, 4 H, ОСН2—CH2—
СН=СН2); 5.87—5.98 (m, 2 H, ОСН2—CH2—СН=СН2);
6.90—7.45 (m, 32 H, H arom.); 7.60—7.72 (m, 2 H, СH=N).
Found (%): С, 74.73; H, 6.57; Cl, 6.21; N, 2.49. C70H72Cl2N2O4Ti.
Calculated (%): С, 74.79; H, 6.46; Cl, 6.31; N, 2.49.
Bis{2ꢀ{[4ꢀ(pentꢀ4ꢀenyloxy)phenylimino]methyl}ꢀ4,6ꢀdiꢀ
(ꢀcumyl)phenoxy}titanium(IV) dichloride (6). The yield was 96%.
IR (KBr), /cm–1: 1609 (C=N), 565 (Ti—O), 469 (Ti—N).
1Н NMR (CDCl3), : 1.40—1.69 (m, 24 Н, CH3); 1.78—1.92
(m, 4 Н, ОСН2—СН2—СН2—СН=СН2); 2.15—2.29 (m, 4 Н,
ОСН2—СН2—СН2—СН=СН2); 3.80—3.99 (m, 4 Н, ОСН2—
СН2—СН2—СН=СН2); 4.99—5.12 (m, 4 Н, ОСН2—СН2—
СН2—СН=СН2); 5.79—5.92 (m, 2 Н, ОСН2—СН2—СН2—
СН=СН2); 6.38—7.56 (m, 32 H, Н arom.); 7.72—7.85 (m, 2 Н,
Н—С=N). Found (%): С, 75.15; H, 6.59; Cl, 5.82; N, 2.48.
C72H76Cl2N2O4Ti. Calculated (%): С, 75.06; H, 6.65; Cl, 6.15;
N, 2.43.
viscosity using the equation19 [] = 6.2•10–4
М
0.7. The molecuꢀ
lar weight characteristics of polymers (Mw and Mw/Mn) were
determined by GPC on an Alliance GPCV2000 chromatograph
(Waters, USA) equipped with styragel columns НТ3 and НТ5
(Waters) at 150 С in 1,2,4ꢀtrichlorobenzene. The thermal propꢀ
erties of the obtained polymers (melting point, enthalpy of phase
transitions) were studied by DSC on a DSCꢀ60 instrument
(Shimadzu). The structures of the obtained polymers were
determined from the IR spectra recorded on a FTIR spectroꢀ
meter (Shimadzu FTIRꢀ8300) in the absorption range from 500
to 2500 cm–1
.
1
The Н NMR spectra of complexes 1—10 were recorded
on a Bruker АVꢀ400 instrument with the working frequency
400.13 MHz. IR spectra were obtained on a Vector 22 spectromꢀ
eter for samples in KBr pellets. Elemental analysis was carried
out on a Euro EA 3000 CHNS analyzer.
Synthesis of complexes 1—10 (general procedure). A mixture of
salicylaldarylimine (2.3 mmol), anhydrous methylene chloride
(10 mL), and a toluene solution (4.25 g) containing TiCl2(OPri)2
(0.273 g, 1.15 mmol) was stirred for 24 h at ambient temperature
under the argon atmosphere. The solvent from the formed dark red
solution was distilled off in a vacuum of a waterꢀjet pump, and
the residue was washed on the filter with hexane (2×2 mL) and
kept for 1 h in a vacuum of an oil pump at 100 С. The correꢀ
sponding complexes were obtained as darkꢀbrown powders.
Bis{2ꢀ[(4ꢀallyloxyphenylimino)methyl]ꢀ6ꢀ(ꢀcumyl)phenꢀ
oxy}titanium(IV) dichloride (1). The yield was 98%. IR (KBr),
/cm–1: 1610 (C=N), 524 (Ti—O), 437 (Ti—N). 1Н NMR
Bis{2ꢀ[(3ꢀallyloxyphenylimino)methyl]ꢀ6ꢀ(ꢀcumyl)phenꢀ
oxy}titanium(IV) dichloride (7). The yield was 89%. IR (KBr),

842
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 4, April, 2012
Ivancheva et al.
/cm–1: 1597 (C=N), 541 (Ti—O), 457 (Ti—N). 1Н NMR
(CDCl3), : 1.49—1.91 (m, 12 Н, СН3); 4.17—4.68 (m, 4 H,
ОСН2—СН=СН2); 5.22—5.44 (m, 4 H, ОСН2—СН=СН2);
5.85—6.11 (m, 2 H, ОСН2—СН=СН2); 6.47—7.62 (m, 24 H,
Н arom.); 7.89—7.96 (m, 2 H, СH=N). Found (%): С, 70.15;
H, 5.82; Cl, 8.00; N, 3.14. C50H48Cl2N2O4Ti. Calculated (%):
С, 69.85; H, 5.63; Cl, 8.25; N, 3.26.
Bis{2ꢀ{[3ꢀ(butꢀ3ꢀenyl)oxyphenylimino]methyl}ꢀ6ꢀ(ꢀcumyl)ꢀ
phenoxy}titanium(IV) dichloride (8). The yield was 93%. IR (KBr),
/cm–1: 1598 (C=N), 541 (Ti—O), 468 (Ti—N). 1Н NMR
(CDCl3), : 1.66—1.81 (m, 12 Н, СН3); 2.47—2.59 (m, 4 H,
ОСН2—CH2—СН=СН2); 3.88—4.07 (m, 4 H, ОСН2—CH2—
СН=СН2); 5.09—5.21 (m, 4 H, ОСН2—CH2—СН=СН2);
5.83—5.95 (m, 2 H, ОСН2—CH2—СН=СН2); 6.64—7.58
(m, 24 H, H arom.); 7.70—7.73 (m, 2 H, СH=N). Found (%):
С, 70.53; H, 6.02; Cl, 7.73; N, 3.06. C52H52Cl2N2O4Ti. Calcuꢀ
lated (%): С, 70.35; H, 5.90; Cl, 7.99; N, 3.16.
Bis{2ꢀ[(3ꢀallyloxyphenylimino)methyl]ꢀ4,6ꢀdi(ꢀcumyl)phenꢀ
oxy}titanium(IV) dichloride (9). The yield was 92%. IR (KBr),
/cm–1: 1596 (C=N), 555 (Ti—O), 470 (Ti—N). 1Н NMR
(CDCl3), : 1.65—1.83 (m, 24 Н, СН3); 4.37—4.54 (m, 4 H,
ОСН2—СН=СН2); 5.25—5.44 (m, 4 H, ОСН2—СН=СН2);
5.89—6.10 (m, 2 H, ОСН2—СН=СН2); 6.39—7.55 (m, 32 H,
Н arom.); 7.77—7.85 (m, 2 H, СH=N). Found (%): С, 74.29;
H, 6.36; Cl, 6.23; N, 2.93. C68H68Cl2N2O4Ti. Calculated (%):
С, 74.52; H, 6.25; Cl, 6.47; N, 2.88.
Bis{2ꢀ{[3ꢀ(butꢀ3ꢀenyl)oxyphenylimino]methyl}ꢀ4,6ꢀdiꢀ
(ꢀcumyl)phenoxy}titanium(IV) dichloride (10). The yield was
91%. IR (KBr), /cm–1: 1598 (C=N), 554 (Ti—O), 470 (Ti—N).
1Н NMR (CDCl3), : 1.66—1.76 (m, 24 Н, СН3); 2.50—2.57
(m, 4 H, ОСН2—CH2—СН=СН2); 3.95—4.04 (m, 4 H, ОСН2—
CH2—СН=СН2); 5.09—5.20 (m, 4 H, ОСН2—CH2—СН=СН2);
5.79—5.93 (m, 2 H, ОСН2—CH2—СН=СН2); 6.72—7.44
(m, 32 H, H arom.); 7.57—7.75 (m, 2 H, СH=N). Found (%):
С, 75.01; H, 6.61; Cl, 6.21; N, 2.46. C70H72Cl2N2O4Ti. Calcuꢀ
lated (%): С, 74.79; H, 6.46; Cl, 6.31; N, 2.49.
The authors are grateful to M. G. Eremeeva for experꢀ
iments on polymerization and to S. Ya. Khaikin and E. V.
Sviridova for the determination of the thermal, structural,
and molecular characteristics of the PE samples.
This work was financially supported by the Siberian
Branch of the Russian Academy of Sciences (Integration
Project No. 123) and the Russian Foundation for Basic
Research (Project No. 11ꢀ03ꢀ12016 ofiꢀmꢀ2011).
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Ethylene polymerization in the presence of the homogeneous
catalysts (bis(phenoxyimine) titanium chloride complexes) and the
catalysts selfꢀimmobilized on PE was carried out in a 200ꢀcm3
reactor. The reactor was loaded through a loading connecting
pipe with a calculated amount of toluene and components of the
catalytic systems (catalyst and MAO) using medical syringes,
and the reaction mixture was saturated with ethylene with simulꢀ
taneous heating to the working temperature (20—60 С) and an
automatically maintained pressure of 0.4 MPa with stirring with
a rate of 1300 rpm. At a certain time interval, the reaction was
stopped by the addition of a deactivating mixture (50 mL of isoꢀ
propyl alcohol and 2—3 mL of hydrochloric acid) to the reaction
medium. The polymer product was filtered off, washed with alcohol
and water, and dried at 60 С in vacuo to a constant weight.
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Received November 18, 2011;
in revised form January 30, 2012