Complexes of titanium(IV) chloride with N-(3,5-R,R′-salicylidene)- 2(3,4)-[bis(5-methyl-2-furyl)methyl]aniline, a novel type of phenoxyimine catalysts for olefin polymerization

Article abstract of DOI:10.1007/s11172-006-0489-3

New representatives of chelate-type titanium(IV) salicylideneaniline complexes with bis(5-methyl-2-furyl)methyl substituents in the aniline fragment are synthesized. In the presence of poly(methylalumoxane), these complexes catalyze ethylene and propylene polymerization. The effect of the position of substituents in the ligands on the activities of the catalysts is studied. High-molecular-weight linear polyethylene (M _w ≈ 172200-300000, M _w/M _n ≈ 2-3) and high-molecular-weight atactic elastic polypropylene (M _w ≈ 1000000, M _w/M _n ≥ 7.0) are obtained.

Full text of DOI:10.1007/s11172-006-0489-3

Russian Chemical Bulletin, International Edition, Vol. 55, No. 10, pp. 1794—1802, October, 2006
1794
Complexes of titanium(IV) chloride with Nꢀ(3,5ꢀR,R´ꢀsalicylidene)ꢀ
2(3,4)ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline, a novel type
of phenoxyimine catalysts for olefin polymerization
S. Ch. Gagieva,a T. A. Sukhova,b D. V. Savinov,c V. A. Tuskaev,a K. A. Lyssenko,d
N. M. Bravaya,b Yu. N. Belokon´,d and B. M. Bulychevaꢀ
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: B.Bulychev@highp.chem.msu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
5 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 515 5420. Eꢀmail: nbravaya@cat.icp.ac.ru
cN. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences,
4 ul. Kosygina, 119991 Moscow, Russian Federation.
Fax: +7 (495) 137 8318
dA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5085. Eꢀmail: yubel@ineos.ac.ru
New representatives of chelateꢀtype titanium(IV) salicylideneaniline complexes with
bis(5ꢀmethylꢀ2ꢀfuryl)methyl substituents in the aniline fragment are synthesized. In the presꢀ
ence of poly(methylalumoxane), these complexes catalyze ethylene and propylene polymerizaꢀ
tion. The effect of the position of substituents in the ligands on the activities of the catalysts is
studied. Highꢀmolecularꢀweight linear polyethylene (Mw ≈ 172200—300000, Mw/Mn ≈ 2—3)
and highꢀmolecularꢀweight atactic elastic polypropylene (Mw ≈ 1000000, Mw/Mn ≥ 7.0) are
obtained.
Key words: titanium(IV) chlorides, oxoimine ligands, homogeneous catalysis, polymerizaꢀ
tion, olefins, polyethylene, polypropylene.
A new class of olefin polymerization catalysts based
tion metal and an inorganic and/or organic ligand.11—13
Therefore, the concept of design of novel complexes beꢀ
longing to postꢀmetallocene catalysts is based on variaꢀ
tions of the electron density in the ligand molecules toꢀ
gether with the steric crowding of the active sites.14—16
Both these effects are reached upon introduction of diꢀ
verse substituents into the ligands. On the other hand, the
possibility of modification of a counterꢀion, which can
also control the catalytic activity of a system, is employed
to a much lesser extent. Processes associated with the
formation of contact ion pairs or zwitterꢀions, which can
be obtained, e.g., upon coordination of poly(methylꢀ
alumoxane) (MAO) to precursor complexes through
salicylideneaniline ligands, can be regarded as possible
trends in this direction. Considering the ease of formaꢀ
tion of aluminum donorꢀacceptor complexes with oxyꢀ
genꢀcontaining ligands, one can regard bis(5ꢀmethylꢀ
2ꢀfuryl)methyl substituents with two oxygen atoms
that can be involved in the coordination as potenꢀ
tial bridges between the transition metal sites and the
counterꢀions.
on the Group 4 transition metals and phenoxyimine
ligands arouse steady interest since the first publicaꢀ
tions.1—4 The attention to these catalytic systems is due to
inherent unique properties. Thus various types of polyꢀ
olefins, viz., superhighꢀmolecularꢀweight polyethylene
(PE), lowꢀmolecularꢀweight PE with terminal vinyl
groups, highly regular isotactic and syndiotactic polyꢀ
propylene (PP), highꢀmolecularꢀweight atactic PP,
poly(αꢀolefins), superhighꢀmolecularꢀweight random and
blockꢀcopolymers of ethylene with propylene, ethylene —
norbornene, and some others, have been prepared using
these catalysts.5—10 Some of them enable 'living' polymerꢀ
ization of ethylene and propylene even at high temperaꢀ
tures yielding PE and PP with very narrow molecularꢀ
weight distribution (Mw/Mn ≈ 1; where Mw and Mn are
weightꢀaverage and numberꢀaverage molecular weights,
respectively), which is one of their most interesting propꢀ
erties.
Currently, it is generally accepted that the active site
of a Zieglerꢀtype catalyst comprises a cation of a transiꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1730—1737, October, 2006.
1066ꢀ5285/06/5510ꢀ1794 © 2006 Springer Science+Business Media, Inc.

Ti complexes as catalysts for olefin polymerization
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1795
Scheme 1
In the present work, we describe synthesis of three
groups of Schiff base derivatives containing orthoꢀ,
metaꢀ and paraꢀbis(5ꢀmethylꢀ2ꢀfuryl)methyl substituents
in the aniline moieties of ligands as well as studies on
catalytic properties of the respective TiIV complexes in
homogeneous polymerization of ethylene and propylene.
Results and Discussion
2,2´ꢀ(2ꢀNitrophenyl)methylidenedi(5ꢀmethylfuran)
(1a), 2,2´ꢀ(3ꢀnitrophenyl)methylidenedi(5ꢀmethylfuran)
(1b), and 2,2´ꢀ(4ꢀnitrophenyl)methylidenedi(5ꢀmethylꢀ
furan) (1с) were obtained by reactions of the correspondꢀ
ing nitrobenzaldehydes with 2ꢀmethylfuran in the presꢀ
ence of chlorotrimethylsilane. Their reduction with soꢀ
dium borohydride in the presence of Pd/C afforded
bis(5ꢀmethylꢀ2ꢀfuryl)methylanilines 2а—с (Sheme 1).
1: 2ꢀNO2 (a), 3ꢀNO2 (b), 4ꢀNO2 (c)
2: 2ꢀNH2 (a), 3ꢀNH2 (b), 4ꢀNH2 (c)
1
Signals for the aromatic protons in the H NMR spectra
of compounds 1a,b and 2a,b appear as multiplets.
Reactions of the aniline derivatives 2a—c with the
corresponding salicylaldehyde derivatives yield the tarꢀ
get Nꢀ(3,5ꢀR,R´ꢀsalicylidene)ꢀ2(3,4)ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]anilines 3—17 (Scheme 2).
Xꢀray diffraction analysis of compound 6 gave addiꢀ
tional information on the structures of the synthesized
compounds (Fig. 1, Table 1).
In the crystal of compound 6, the hydroxy group of
the salicylaldehyde fragment is involved in intramolecuꢀ
lar Hꢀbonding N...H—O (N(1)...O(1), d 2.600(2) Å) with
closure of a planar sixꢀmembered ring. The phenyl ring
of the amine is somewhat turned around with respect
Reagents and conditions: i. ClSiMe3. ii. NaBH4, Pd/C, MeOH.
to the salicylaldimine fragment with a torsion angle
С(8)—N(1)—C(9)—C(14) of 34.1°. The bisector plane of
the bis(5ꢀmethylꢀ2ꢀfuryl)methyl fragment is virtually coꢀ
planar with the phenyl ring. The corresponding bond
lengths in the furan rings are the same and are close to
those expected for this class of compounds. The bond
angles С(21)—С(15)—С(16) and С(21)—С(15)—С(11)
are somewhat enlarged (to 113.9(1)°) as compared with
the standard values.
Scheme 2
Comꢀ
pound
R1 R2
Comꢀ
pound
R1
R2
Comꢀ
pound
R1
Br
Me Br
Br OMe
R2
Comꢀ
pound
R1
R2
Comꢀ
pound
R1
R2
3
4
5
H
H
Cl
I
6
7
8
H
Cl
Br
Me
Cl
Br
9
10
11
Me
12
13
14
H
NO2
15
16
17
But
Me
But
But
Br
But
H
H
But But
Me Br

1796
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
Gagieva et al.
C(25)
C(23)
C(24)
C(22)
O(3)
C(13)
C(12)
C(7)
C(6)
C(8)
C(1)
C(21)
C(14)
C(9)
C(15)
C(10)
C(11)
C(5)
C(4)
N(1)
C(16)
O(2)
C(2)
C(3)
C(17)
C(18)
C(19)
O(1)
C(20)
Fig. 1. Structure of Nꢀ(5ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline (6).
Table 1. Selected bond lengths (d) and bond angles (ω) in structure 6
Bond
d/Å
Bond
d/Å
Angle
ω/deg
O(1)—C(2)
O(2)—C(16)
O(2)—C(19)
O(3)—C(21)
O(3)—C(24)
N(1)—C(8)
N(1)—C(9)
C(1)—C(2)
C(1)—C(8)
C(15)—C(21)
1.358(2)
1.375(2)
1.381(2)
1.376(2)
1.383(2)
1.286(2)
1.418(2)
1.416(2)
1.454(2)
1.501(2)
C(15)—C(16)
C(16)—C(17)
C(17)—C(18)
C(18)—C(19)
C(19)—C(20)
C(21)—C(22)
C(22)—C(23)
C(23)—C(24)
C(24)—C(25)
1.500(2)
1.340(3)
1.430(3)
1.334(3)
1.481(3)
1.346(3)
1.420(3)
1.337(3)
1.479(3)
C(16)—O(2)—C(19)
C(21)—O(3)—C(24)
C(8)—N(1)—C(9)
C(6)—C(1)—C(2)
N(1)—C(8)—C(1)
C(21)—C(15)—C(16)
C(21)—C(15)—C(11)
C(16)—C(15)—C(11)
106.43(15)
107.04(15)
121.01(15)
118.50(16)
121.87(16)
113.90(14)
113.94(14)
109.64(15)
Despite transꢀarrangement of the O(2) and
O(3) atoms of the furan rings with a pseudotorsion angle
О(2)—С(16)—С(21)—О(3) of 104.0°, the analysis of inꢀ
tramolecular contacts shows the lack of steric hindrance
in the molecule for cisꢀarrangement of these atoms as
well. Presumably, the conformation in the crystal 6 is
determined by weak intermolecular contacts of the
С—H...О type. Hence, one may suggest that the oxyꢀ
gen atoms are the more so prone to the coordination
with MAO.
We prepared dichloride complexes of titanium(IV)
with Nꢀ(3,5ꢀR,R´ꢀsalicylidene)ꢀ2(3,4)ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline by a known procedure17 from titaꢀ
nium dichloride diisopropoxide and the corresponding
ligand in dry dichloromethane (Scheme 3). By analogy
with the known data18,19 on the structures of oxoimine
chloride complexes, we believe that compounds 18—32
prepared by us possess similar structures. Data from elꢀ
emental analyses, 1H NMR spectroscopy (compound 32),
and IR spectroscopy corroborate their structures. The
IR spectra demonstrate a bathochromic shift of the band
ν(С=N) by 15—22 cm–1 as compared with the spectrum
of the free ligand. In addition, new bands appear at 450—
570 cm–1, which can be attributed to stretching vibrations
of the Ti—N and Ti—O bonds. In the 1H NMR spectrum,
the characteristic signal for the aldimine protons is a sinꢀ
glet, which suggests their equivalence and C2ꢀsymmetry
of the complex.
The catalytic properties of complexes 18—32 in ethylꢀ
ene polymerization were studied in reactions carried out
at 30 °С and atmospheric pressure of the monomer with
MAO as a coꢀcatalyst at an AlMAO/Ti ratio ≈ 500.
The effect of the character and position of substituents
in the ligands on the catalytic activities of the complexes
is presented in Table 2.
As can be seen from Table 2, complexes 18—21, poorly
soluble in toluene, manifest very low catalytic activiꢀ
ties. The introduction of two halogen atoms in the ligand
increases the solubilities of complexes 22 and 23. The
yellow color of solutions of these complexes in toluene
fades upon addition of MAO, which suggests their effiꢀ
cient alkylation (see Ref. 20); however, these complexes
produce only trace amounts of PE in the catalytic reꢀ
action.

Ti complexes as catalysts for olefin polymerization
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1797
Scheme 3
Transmission (%)
1
60
2
50
40
1368
1380
1340
1300
ν/cm–1
Fig. 2. Fragments of the IR spectra of PE obtained on catalysts
24 (1) and 32 (2).
meric chain that is growing (or is formed) at the acꢀ
tive site.
Polyethylene specimens obtained on catalysts 24, 25,
31 and 32 have linear structures, which is supported by
data from IR spectra of the polymers (Fig. 2) where no
bands of the deformation vibrations of the methyl groups
in branchings (1378 cm–1 23
) were present. These PE speciꢀ
mens manifest virtually identical GPC patterns (Fig. 3).
Catalytic properties of a system 32—MAO in propyꢀ
lene polymerization are given in Table 3. It can be seen
that the reduced activity of the system in the liquid monoꢀ
mer medium at 50 °С (Table 3, entry 3) is 500 times lower
than in ethylene polymerization. It should be mentioned
that a much lesser decrease in reduced activity (ca. twoꢀ
fold) on going from ethylene polymerization to propylene
polymerization has been observed21 for a series of strucꢀ
turally similar titanium phenoxyimine complexes.
Comꢀ R1
plex
R2
Comꢀ
plex
R1
Br
Br
Me
Br
H
R2
Br
Me
Br
Comꢀ
plex
R1
R2
18
19
20
21
22
H
H
H
H
Cl
H
Cl
I
Me
Cl
23
24
25
26
27
28
29
30
31
32
But
Me
But
Me
But
But
Br
But
Br
The results of diffractometric and 13С NMR spectroꢀ
scopic studies of polypropylene24 obtained with the use of
OMe
NO2
But
dW/d(logMw)
Simultaneous introduction of a bromine atom and a
Me group in positions 3 and 5 of the salicylaldehyde fragꢀ
ment (complexes 24 and 25) increases their integral activꢀ
ity to 1120 and 1733 kg PE (mol Ti h [C2H4])–1, respecꢀ
tively. Complexes 29 and 31 with oꢀ and pꢀbis(5ꢀmethylꢀ
2ꢀfuryl)methyl substituents in the ligands are less acꢀ
tive than complex 25 with the same substituent in the
metaꢀposition.
1.0
1
2
0.8
3
4
0.6
Of the compounds obtained, that with tertꢀbutyl subꢀ
stituents (complex 32) possessed the highest activity.
As can be seen from Table 2, this is only 1.5—2ꢀfold
lower than that of the known recordꢀholder among simiꢀ
lar compounds, viz., titanium bis(3,5ꢀdiꢀtertꢀbutylsalicylꢀ
idene)ꢀ2,3,5,6ꢀtetrafluoroanilinate.21,22 It is of note that
complexes 30 and 28 with oꢀ and mꢀbis(5ꢀmethylꢀ2ꢀ
furyl)methyl substituents in the ligand (the isomers of
complex 32) afford only trace amounts of PE. Presumꢀ
ably, this is related to steric crowding at the metal atom,
which hampers approach of the monomer to the polyꢀ
0.4
0.2
4.0
4.5
5.0
5.5
6.0
logMw
Fig. 3. Molecularꢀmass distribution of PE obtained on catalysts
24 (1), 25 (2), 31 (3), and 32 (4).

1798
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
Gagieva et al.
Table 2. Structures of the starting ligands and catalytic activities of complexes 18—32 in polymerization of ethylene
(МАО as a cocatalyst , AlMAO/Ti = 500 mol mol–1, toluene, reaction temperature 30 °С, total pressure of ethylene
and toluene vapor, 1 atm)
Liꢀ
gand
R1
R2
Compꢀ
lex
Ti•106
/mol
t
Y
/g
A/kg PE
(mol Ti h [C2H4])–1
Mw
Mw/Mn
/min
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
17
17
H
H
H
H
Cl
Br
Br
Me
Br
NO2
But
Me
But
Me
But
But
But
H
Cl
I
Me
Cl
Br
Me
Br
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
32
32
3.6
2.8
3.6
3.6
3.6
3.6
8.8
3.6
3.6
8.7
2.6
3.6
2.9
2.6
2.8
1.1
0.14
30
30
30
30
30
35
19
30
29
16
60
30
30
30
7
0.01
0.01
0.06
0.01
0.01
0.06
0.39
0.39
0.01
0.01
0.01
0.01
0.02
0.10
0.47
0.34
0.06
44
57
267
44
—
—
—
—
—
—
—
—
—
—
44
229
1120
1733
44
44
44
—
—
199000
172200
—
—
—
—
—
180600
306000
—
2.34
2.64
—
—
—
—
—
2.73
2.12
—
OMe
H
But
Br
44
But
Br
110
615
11510
7418
4114
But
But
But
20
50
—
—
Note. Here and in Table 3, t is polymerization time, Y is yield of polymer, A is integral activity, Mw and Mn are weightꢀ
average and numberꢀaverage molecular weights, respectively.
tactic blocks separated by atactic sequences.27 Attention
should be paid to the fact that no rupture of samples of
highꢀmolecularꢀmass atactic PP on their ca. 20ꢀfold elonꢀ
gation was observed.
Table 3. Bulk polymerization of propylene on a catalytic system
32—МАО at 30 °С
Entry [Ti]•105
AlMAO/Ti t/h Y/g Аa
Mw
Mw
/mol L–1 /mol mol–1
/Mn
Thus, we have synthesized three groups of Schiff base
derivatives containing the bis(5ꢀmethylꢀ2ꢀfuryl)methyl
substituent in the oꢀ, mꢀ, and pꢀpositions of the aniline
moiety of the ligand. In the presence of polymethylꢀ
alumoxane, titanium complexes with these ligands beꢀ
have as catalysts of ethylene and propylene polymerizaꢀ
tion. The incorporation of the bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl substituent enhances the catalytic activity as comꢀ
pared with conventional phenoxyimine catalysts.28 The
results obtained are in keeping with a suggestion that
the enhancement of activities of complexes comprising
bis(5ꢀmethylꢀ2ꢀfuryl)methyl substituents can be rationalꢀ
ized by coordination of the oxygen atoms of the furan
rings to organoaluminum compounds resulting in, at the
least, a contact ion pair.
1 b
2.31
2.26
2.28
1800
600
600
1.2 9.3 153 1.2•106 7.6
1.2 6.4 105 2.0•106 9.8
4.3 4.3
2 c
3 с,d
23 2.0•106 9.8
а Reduced activity in kg PP (mol Ti h [C3H6])–1
b The catalyst was added as a solution in 10% solution of МАО
.
in toluene.
c The catalyst was added as a solid.
d At 50 °С.
the system 32—MAO suggest the formation of atactic
(radioamorphous) polymer containing ca. 5 mol.% of
regioerrors (viz., 2,1ꢀadditions) (δС 16—17). Moreover,
the distribution of the methyl pentads in this polymer is
similar to that in an 'ideal' atactic PP. Polypropylene with
analogous properties has been obtained on other structurꢀ
ally similar catalysts studied by us earlier.25,26
Experimental
The atactic PP synthesized on the system 32—MAO
has high molecular mass (ca. 107) and broad molecularꢀ
mass distribution (Mw/Mn = 7—10). In addition, the polyꢀ
mer possessed properties of an elastomer: the residual
elongation following stretching by 300% (ε300) did not
exceed 21%. In these parameters, the polypropylene obꢀ
tained by us is analogous to elastomeric stereoꢀblock
polypropylene composed of short isotactic and syndioꢀ
The complexes were synthesized in an atmosphere of argon.
Tetrahydrofuran, dichloromethane, toluene, propanꢀ2ꢀol,
hexane, and ethyl acetate (chemically pure) were additionally
purified according to known procedures.29 Titanium(IV) chloꢀ
ride (Fluka) was additionally distilled under argon. Commercial
SiO2, 2ꢀ, 3ꢀ, and 4ꢀnitrobenzaldehydes, 2ꢀmethylfuran, and
chlorotrimethylsilane (Fluka) were used. NMR spectra of the
ligands in CDCl3 were recorded on Bruker WPꢀ200 and Bruker

Ti complexes as catalysts for olefin polymerization
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1799
АМХꢀ400 spectrometers and IR spectra, on a MagnaꢀIR 750
spectrophotometer. Elemental analyses were carried out on Carlo
Erbaꢀ1106 and Carlo Erbaꢀ1108 instruments.
Ligands 4—17 were obtained analogously.
Nꢀ(5ꢀChlorosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline (4). The yield was 81%. Found (%): С, 70.85; H, 4.50;
N, 2.97. С24H20ClNO3. Calculated (%): С, 71.02; H, 4.97;
N, 3.45. 1Н NMR, δ: 2.20 (s, 6 H, Me); 5.80 (m, 4 H, Hfur); 5.90
(s, 1 H, CH); 6.90—7.40 (m, 7 H, HAr); 8.60 (s, 1 H, CH=N);
11.59 (s, 1 H, OH).
Nꢀ(5ꢀIodosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniꢀ
line (5). The yield was 75%. Found (%): С, 57.70; H, 4.08;
N, 2.70. С24H20INO3. Calculated (%): С, 57.96; H, 4.50;
N, 2.97. 1H NMR, δ: 2.18 (s, 6 H, Me); 5.82 (m, 4 H, Hfur); 5.84
(s, 1 H, CH); 6.50—7.80 (m, 7 H, HAr); 8.46 (s, 1 H, CH=N);
11.50 (s, 1 H, OH).
Nꢀ(5ꢀMethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline (6). The yield was 81%. Found (%): С, 70.85; H, 4.50;
N, 2.97. С25H23NO3. Calculated (%): С, 71.02; H, 4.97; N, 3.45.
1H NMR, δ: 2.20 (s, 6 H, Me); 2.38 (s, 3 H, Me); 5.80 (m, 4 H,
fur); 5.90 (s, 1 H, CH); 6.90—7.40 (m, 7 H, HAr); 8.60 (s, 1 H,
CH=N); 11.59 (s, 1 H, OH).
2,2´ꢀ(3ꢀNitrophenyl)methylenedi(5ꢀmethylfuran) (1b). Chloꢀ
rotrimethylsilane (2 mL) was added to a solution of 3ꢀnitroꢀ
benzaldehyde (15 g, 0.1 mol) and 2ꢀmethylfuran (18 g, 20 mL,
0.22 mol) in benzene (60 mL). After 2—3 h, water was added
to the reaction mixture, the organic layer was washed with
3% NaHCO3, concentrated and the residue recrystallized from
hexane. The yield was 15.3 g (47%), m.p. 95—96 °C. Found (%):
С, 68.57; H, 4.89; N, 4.58. C17H15NO4. Calculated (%):
С, 68.68; H, 5.09; N, 4.71. 1H NMR, δ: 2.17 (s, 6 H, Me);
5.76 (m, 4 H, Hfur); 5.80 (s, 1 H, СН); 7.99, 8.00 (both m,
2 H each, 2 HAr).
Compounds 1а,c were obtained analogously.
2,2´ꢀ(2ꢀNitrophenyl)methylenedi(5ꢀmethylfuran) (1a). The
yield was 18.0 g (55%), m.p. 83—84 °C. Found (%): С, 68.46;
H, 4.76; N, 4.60. C17H15NO4. Calculated (%): С, 68.68; H, 5.09;
N, 4.71. 1H NMR, δ: 2.20 (s, 6 H, Me); 5.87 (m, 4 H, Hfur); 5.92
(s, 1 H, СН); 7.80, 8.10 (both m, 2 H each, HAr).
2,2´ꢀ(4ꢀNitrophenyl)methylenedi(5ꢀmethylfuran) (1с). The
yield was 19.7 g (64%), m.p. 89—91 °C. Found (%): С, 68.50;
H, 4.80; N, 4.65. C17H15NO4. Calculated (%): С, 68.68; H, 5.09;
N, 4.71. 1H NMR, δ: 2.20 (s, 6 H, Me); 5.80 (m, 4 H,
H
Nꢀ(3,5ꢀDichlorosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline (7). The yield was 76%. Found (%): С, 65.08; H, 4.18;
N, 2.90. С24H19Cl2NO3. Calculated (%): С, 65.47; H, 4.35;
N, 3.18. 1H NMR, δ: 2.23 (s, 6 H, Me); 5.80 (m, 4 H, Hfur); 5.90
(s, 1 H, CH); 7.10—7.30 (m, 6 H, HAr); 8.60 (s, 1 H, CH=N);
11.59 (s, 1 H, OH).
H
fur); 5.85 (s, 1 H, СН); 7.50, 8.00 (both d, 2 H each, HAr
,
J = 8.9 Hz).
Nꢀ(3,5ꢀDibromosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline (8). The yield was 82%. Found (%): С, 54.12; H, 3.20;
N, 2.50. С24H19Br2NO3. Calculated (%): С, 54.47; H, 3.62;
N, 2.65. 1H NMR, δ: 2.18 (s, 6 H, Me); 5.80 (m, 4 H, Hfur); 5.85
(s, 1 H, CH); 7.10—7.60 (m, 6 H, HAr); 8.40 (s, 1 H, CH=N);
11.60 (s, 1 H, OH).
3ꢀ[Bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline (2b). To a solution
of compound 1b (3.00 g, 0.01 mol) in hot MeOH (70 mL),
10% Pd/C (0.50 g) was added followed by NaBH4 (0.82 g,
0.02 mol), which was added in small portions with vigorous
stirring. After 15 min, the mixture was filtered, the filtrate was
concentrated in vacuo, the residue was triturated with ether and
the extract was concentrated on a rotary evaporator. The oily resiꢀ
due was purified by column chromatography (hexane—AcOEt,
5 : 1) to give compound 2b as yellow oil in a yield of 2.9 g
(89.5%). Found (%): С, 76.19; H, 6.28; N, 5.18. C17H17NO2.
Calculated (%): С, 76.38; H, 6.41; N, 5.24. 1H NMR, δ: 2.17 (s,
6 H, Me); 5.76 (m, 4 H, Hfur); 5.80 (s, 1 H, CH); 6.45, 6.89
(both m, 2 H each, HAr).
Nꢀ(3ꢀBromoꢀ5ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline (9). The yield was 81%. Found (%): С, 64.32;
H, 4.26; N, 2.80. С25H22BrNO3. Calculated (%): С, 64.66;
1
H, 4.78; N, 3.02. H NMR, δ: 2.20 (s, 6 H, Me); 5.80 (m, 4 H,
Hfur); 5.83 (s, 1 H, CH); 7.10—7.20 (m, 6 H, HAr); 8.40 (s, 1 H,
CH=N); 11.80 (s, 1 H, OH).
Nꢀ(5ꢀBromoꢀ3ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline (10). The yield was 78%. Found (%):
С, 64.32; H, 4.26; N, 2.80. С25H22BrNO3. Calculated (%):
С, 64.66; H, 4.78; N, 3.02. 1H NMR, δ: 2.20 (s, 6 H, Me); 5.80
(m, 4 H, Hfur); 5.83 (s, 1 H, CH); 7.10—7.19 (m, 6 H, HAr);
8.36 (s, 1 H, CH=N); 11.90 (s, 1 H, OH).
Compounds 2а,c were obtained analogously.
2ꢀ[Bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline (2а). The yield was
2.5 g (78%). Found (%): С, 76.03; H, 6.20; N, 5.07. C17H17NO2.
Calculated (%): С, 76.38; H, 6.41; N, 5.24. 1H NMR, δ: 2.20 (s,
6 H, Me); 5.60 (m, 4 H, Hfur); 5.78 (s, 1 H, CH); 6.65, 6.98
(both m, 2 H each, HAr).
4ꢀ[Bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline (2c). The yield was
3.0 g (92.6%). Found (%): С, 76.19; H, 6.14; N, 4.99.
C17H17NO2. Calculated (%): С, 76.38; H, 6.41; N, 5.24.
1H NMR, δ: 2.25 (s, 6 H, Me); 5.66 (m, 4 H, Hfur); 5.85 (s, 1 H,
CH); 6.78, 7.07 (both d, 2 H each, HAr).
Nꢀ(Salicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)methyl]aniline (3).
Aniline 2b (0.23 g, 0.85 mmol) and TsOH (0.003 g, 0.02 mmol)
were added to a solution of salicylaldehyde (0.10 g, 0.85 mmol),
the mixture was refluxed with stirring for 20 h, filtered, the
filtrate was concentrated and chromatographed on a column
with silica gel (hexane—AcOEt, 5 : 1) to give compound 3 as
yellow crystals in a yield of 0.26 g (87%). Found (%): С, 77.15;
H, 5.81; N, 3.30. С24H21NO3. Calculated (%): С, 77.61; H, 5.70;
N, 3.77. 1H NMR, δ: 2.30 (s, 6 H, Me); 5.60 (m, 4 H, Hfur); 5.87
(s, 1 H, CH); 7.10—7.45 (m, 8 H, HAr); 8.39 (s, 1 H, CH=N);
11.79 (s, 1 H, OH).
Nꢀ(3ꢀBromoꢀ5ꢀmethoxysalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline (11). The yield was 72%. Found (%):
С, 62.02; H, 4.21; N, 2.65. С25H22BrNO4. Calculated (%):
С, 62.51; H, 4.62; N, 2.92. 1H NMR, δ: 2.20 (s, 6 H, Me); 3.80
(s, 3 H, ОMe); 5.80 (m, 4 H, Hfur); 5.83 (s, 1 H, CH); 6.90—7.13
(m, 6 H, HAr); 8.30 (s, 1 H, CH=N); 11.70 (s, 1 H, OH).
Nꢀ(3ꢀNitrosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline (12). The yield was 73%. Found (%): С, 69.60;
H, 4.29; N, 6.50. С24H20N2O5. Calculated (%): С, 69.22;
1
H, 4.84; N, 6.73. H NMR, δ: 2.22 (s, 6 H, Me); 5.80 (m, 4 H,
Hfur); 5.97 (s, 1 H, CH); 7.10—7.93 (m, 7 H, HAr); 8.39 (s, 1 H,
CH=N); 11.97 (s, 1 H, OH).
Nꢀ(3,5ꢀDiꢀtertꢀbutylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline (13). The yield was 83%. Found (%):
С, 79.52; H, 7.60; N, 2.70. С32H37NO3. Calculated (%):
С, 79.47; H, 7.71; N, 2.90. 1H NMR, δ: 1.45 (s, 18 H, Me); 2.14
(s, 6 H, Me); 5.80 (m, 4 H, Hfur); 5.85 (s, 1 H, CH); 7.10—7.60
(m, 6 H, HAr); 8.40 (s, 1 H, CH=N); 11.70 (s, 1 H, OH).

1800
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
Gagieva et al.
Nꢀ(5ꢀBromoꢀ3ꢀmethylsalicylidene)ꢀ2ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline (14). The yield was 72%. Found (%):
С, 64.32; H, 4.26; N, 2.80. С25H22BrNO3. Calculated (%):
С, 64.66; H, 4.78; N, 3.02. 1H NMR, δ: 2.20 (s, 6 H, Me); 5.80
(m, 4 H, Hfur); 5.83 (s, 1 H, CH); 7.10—7.19 (m, 6 H, HAr);
8.36 (s, 1 H, CH=N); 11.90 (s, 1 H, OH).
Bis{Nꢀ(3ꢀbromoꢀ5ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline}titanium(IV) dichloride (24). The yield was
74%. Found (%): С, 57.05; H, 3.75; Cl, 6.20; N, 2.40; Ti, 4.39.
С
50H42Br2Cl2N2O6Ti. Calculated (%): С, 57.44; H, 4.05;
Cl, 6.78; N, 2.68; Ti, 4.58. IR, ν/cm–1: 1610 (C=N); 520
(Ti—O); 450 (Ti—N).
Nꢀ(3,5ꢀDiꢀtertꢀbutylsalicylidene)ꢀ2ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline (15). The yield was 71%. Found (%): С, 79.52;
H, 7.60; N, 2.70. С32H37NO3. Calculated (%): С, 79.47; H, 7.71;
N, 2.90. 1H NMR, δ: 1.45 (s, 18 H, Me); 2.14 (s, 6 H, Me); 5.80
(m, 4 H, Hfur); 5.85 (s, 1 H, CH); 7.10—7.60 (m, 6 H, HAr);
8.40 (s, 1 H, CH=N); 11.70 (s, 1 H, OH).
Bis{Nꢀ(5ꢀbromoꢀ3ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline}titanium(IV) dichloride (25). The yield was
77%. Found (%): С, 57.09; H, 3.75; Cl, 6.50; N, 2.54; Ti, 4.30.
С
50H42Br2Cl2N2O6Ti. Calculated (%): С, 57.44; H, 4.05;
Cl, 6.78; N, 2.68; Ti, 4.58. IR, ν/cm–1: 1610 (C=N); 527
(Ti—O); 453 (Ti—N).
Nꢀ(5ꢀBromoꢀ3ꢀmethylsalicylidene)ꢀ4ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline (16). The yield was 75%. Found (%): С, 64.32;
H, 4.26; N, 2.80. С25H22BrNO3. Calculated (%): С, 64.66;
H, 4.78; N, 3.02. 1H NMR, δ: 2.20 (s, 6 H, Me); 5.80 (m, 4 H,
Hfur); 5.83 (s, 1 H, CH); 7.10—7.19 (m, 6 H, HAr); 8.36 (s, 1 H,
CH=N); 11.90 (s, 1 H, OH).
Bis{Nꢀ(3ꢀbromoꢀ5ꢀmethoxysalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline}titanium(IV) dichloride (26). The yield was
75%. Found (%): С, 55.40; H, 3.80; Cl, 6.49; N, 2.50; Ti, 4.12.
С
50H42Br2Cl2N2O8Ti. Calculated (%): С, 55.74; H, 3.93; Cl,
6.58; N, 2.60; Ti, 4.44. IR, ν/cm–1: 1615 (C=N); 528 (Ti—O);
443 (Ti—N).
Nꢀ(3,5ꢀDiꢀtertꢀbutylsalicylidene)ꢀ4ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline (17). The yield was 85%. Found (%): С, 79.52;
H, 7.60; N, 2.70. С32H37NO3. Calculated (%): С, 79.47; H, 7.71;
N, 2.90. 1H NMR, δ: 1.45 (s, 18 H, Me); 2.14 (s, 6 H, Me); 5.80
(m, 4 H, Hfur); 5.85 (s, 1 H, CH); 7.10—7.60 (m, 6 H, HAr);
8.40 (s, 1 H, CH=N); 11.70 (s, 1 H, OH).
Bis{Nꢀ(3ꢀnitrosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline}titanium(IV) dichloride (27). The yield was 65%.
Found (%): С, 60.51; H, 3.83; Cl, 7.20; N, 2.40; Ti, 4.74.
С48H38Cl2N4O10Ti. Calculated (%): С, 60.71; H, 4.03; Cl, 7.47;
N, 2.58; Ti, 5.04. IR, ν/cm–1: 1612 (C=N); 524 (Ti—O);
450 (Ti—N).
Synthesis of complex 18. To a solution of compound 3 (0.37 g,
0.10 mmol) in CH2Cl2 (10 mL), TiCl2(OPri)2 (0.12 g,
0.05 mmol) was added with stirring under argon. After 20 h, the
red precipitate was filtered off and recrystallized from toluene.
The yield was 0.73 g (85%). Found (%): С, 66.50; H, 4.60;
Cl, 8.07; N, 3.15; Ti, 5.50. С48H40Cl2N2O6Ti. Calculated (%):
С, 67.08; H, 4.69; Cl, 8.25; N, 3.26; Ti, 5.57. IR, ν/cm–1: 1606
(C=N); 525 (Ti—O); 454 (Ti—N).
Bis{Nꢀ(5ꢀchlorosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline}titanium(IV) dichloride (19). The yield was 68%.
Found (%): С, 61.66; H, 4.00; Cl, 15.01; N, 2.50; Ti, 5.10.
С48H38Cl4N2O6Ti. Calculated (%): С, 62.09; H, 4.13; Cl, 15.31;
N, 3.02; Ti, 5.16. IR, ν/cm–1: 1607 (C=N); 525 (Ti—O);
450 (Ti—N).
Bis{Nꢀ(5ꢀiodosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuryl)meꢀ
thyl]aniline}titanium(IV) dichloride (20). The yield was 75%.
Found (%): С, 51.36; H, 3.11; N, 2.27; Ti, 4.20.
С48H38Cl2I2N2O6Ti. Calculated (%): С, 51.86; H, 3.42; N, 2.52;
Ti, 4.30. IR, ν/cm–1: 1612 (C=N); 520 (Ti—O); 450 (Ti—N).
Bis{Nꢀ(5ꢀmethylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (21). The yield was 73%.
Found (%): С, 67.25; H, 5.13; Cl, 7.43; N, 2.66; Ti, 5.12.
Bis{Nꢀ(3,5ꢀdiꢀtertꢀbutylsalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (28). The yield was 70%.
Found (%): С, 70.76; H, 6.84; N, 2.40. С64H72Cl2N2O2Ti. Calꢀ
culated (%): С, 70.91; H, 6.69; N, 2.58. IR, ν/cm–1: 1616
(C=N); 519 (Ti—O); 454 (Ti—N).
Bis{Nꢀ(5ꢀbromoꢀ3ꢀmethylsalicylidene)ꢀ2ꢀ[bis(5ꢀmethylꢀ
2ꢀfuryl)methyl]aniline}titanium(IV) dichloride (29). The yield
was 75%. Found (%): С, 57.07; H, 3.70; Cl, 6.50; N, 2.52;
Ti, 4.39. С50H42Br2Cl2N2O6Ti. Calculated (%): С, 57.44;
H, 4.05; Cl, 6.78; N, 2.68; Ti, 4.58. IR, ν/cm–1: 1616 (C=N);
517 (Ti—O); 442 (Ti—N).
Bis{Nꢀ(3,5ꢀdiꢀtertꢀbutylsalicylidene)ꢀ2ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (30). The yield was 79%.
Found (%): С, 70.70; H, 6.92; N, 2.50. С64H72Cl2N2O2Ti. Calꢀ
culated (%): С, 70.91; H, 6.69; N, 2.58. IR, ν/cm–1: 1610
(C=N); 517 (Ti—O); 444 (Ti—N).
Bis{Nꢀ(5ꢀbromoꢀ3ꢀmethylsalicylidene)ꢀ4ꢀ[bis(5ꢀmethylꢀ2ꢀ
furyl)methyl]aniline}titanium(IV) dichloride (31). The yield was
68%. Found (%): С, 57.00; H, 4.00; Cl, 6.53; N, 2.50; Ti, 4.50.
С
50H42Br2Cl2N2O6Ti. Calculated (%): С, 57.44; H, 4.05;
Cl, 6.78; N, 2.68; Ti, 4.58. IR, ν/cm–1: 1607 (C=N); 522
(Ti—O); 455 (Ti—N).
С
50H44Cl2N2O6Ti. Calculated (%): С, 67.65; H, 5.00; Cl, 7.99;
Bis{Nꢀ(3,5ꢀdiꢀtertꢀbutylsalicylidene)ꢀ4ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (32). The yield was 72%.
Found (%): С, 70.83; H, 6.85; N, 2.50. С64H72Cl2N2O2Ti. Calꢀ
culated (%): С, 70.91; H, 6.69; N, 2.58. IR, ν/cm–1: 1610
(C=N); 517 (Ti—O); 447 (Ti—N). 1H NMR (tolueneꢀd6), δ:
1.35 (s, 36 H, Me); 2.14 (s, 12 H, Me); 5.80 (m, 8 H, HAr); 5.85
(s, 2 H, CH); 7.10—7.60 (m, 12 H, HAr); 8.15 (s, 2 H, CH=N).
Xꢀray diffraction study of compound 6 (C25H23NO3) was carꢀ
ried out on an automated Smart CCD 1000K threeꢀcircle
diffractometer at 120 K (MoꢀKα radiation, graphite monochroꢀ
mator, ω scan mode, 2θmax = 58°). The crystals are triclinic: a =
6.145(1) Å, b = 11.869(3) Å, c = 14.317(3) Å, α = 73.716(5)°,
N, 3.16; Ti, 5.39. IR, ν/cm–1: 1610 (C=N); 525 (Ti—O);
452 (Ti—N).
Bis{Nꢀ(3,5ꢀdichlorosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (22). The yield was 75%.
Found (%): С, 57.30; H, 3.24; Cl, 21.03; N, 2.21; Ti, 4.30.
С
48H36Cl6N2O6Ti. Calculated (%): С, 57.80; H, 3.64; Cl, 21.33;
N, 2.81; Ti, 4.80. IR, ν/cm–1: 1614 (C=N); 515 (Ti—O);
455 (Ti—N).
Bis{Nꢀ(3,5ꢀdibromosalicylidene)ꢀ3ꢀ[bis(5ꢀmethylꢀ2ꢀfuꢀ
ryl)methyl]aniline}titanium(IV) dichloride (23). The yield was 79%.
Found (%): С, 48.76; H, 2.90; Cl, 5.80; N, 2.25; Ti, 3.87.
С
48H36Br4Cl2N2O6Ti. Calculated (%): С, 49.06; H, 3.09;
β = 86.733(5)°, γ = 83.066(5)°, V = 994.6(4) Å3, dcalc
=
Cl, 6.03; N, 2.38; Ti, 4.07. IR, ν/cm–1: 1617 (C=N); 522
1.287 g cm–3, M = 385.44, F(000) = 408, µ = 0.84 cm–1, Z = 2
–
(Ti—O); 446 (Ti—N).
(Z´ = 1), space group P1. On the whole, 6705 reflections were

Ti complexes as catalysts for olefin polymerization
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 10, October, 2006
1801
measured (Rint = 0.0177), 5105 of independent reflections were
used in subsequent calculations and refinement. The structure
was solved by the direct method and refined by the fullꢀmatrix
leastꢀsquares method in the anisotropic approximation based
on F 2hkl. The hydrogen atoms were localized from the difference
Fourier syntheses of the electron densities and included in the
final refinement in the isotropic approximation. The final diverꢀ
gence factors are: R = 0.0536 over 3151 reflections with I > 2σ(I ),
wR2 = 0.1164 and goodnessꢀofꢀfit 1.015 over all reflections. All
calculations were performed using the SHELXTL PLUS proꢀ
gram package.30
Ethylene polymerization. In catalytic reactions on ethylene
polymerization, 'special purity' grade toluene was used. The solꢀ
vents were purified from possible admixtures according to known
procedures.25 Polymethylalumoxane (Witco) was used as a
10% solution in toluene. Argon and ethylene (high purity grade)
were dried by passing the gases through columns filled with
molecular sieves 5Å. All procedures for the assembly of the
reactor and the protocol of the pretreatment and introduction of
complexes and gaseous ethylene into the reactor, as well as the
measurement of the polymerization kinetics were described earꢀ
lier.26 After complete dissolution of ethylene in a solution of the
tested complex in toluene or hexane, polymerization was started
by introducing a solution of the catalyst into the reactor and
stopped by adding, to the reactor, 10% ethanolic hydrogen chloꢀ
ride. The polymeric product was filtered off, washed with ethaꢀ
nol and water, and dried in vacuo at 50—60 °C to a constant
weight.
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Propylene polymerization. Polymerization was carried out by
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≈
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Org. Chem. Jpn, 2003, 61, 1124.
16. M. Mitani, J. Saito, S.ꢀI. Ishii, Y. Nakayama, H. Makio,
N. Matsukawa, S. Matsui, J.ꢀI. Mohri, R. Furuyama,
H. Terao, H. Bando, H. Tanaka, and T. Fujita, Chem. Rec.,
2004, 4, 137.
3
6
40 atm) of the polymerization purity grade (99.7 vol.%), which
was used without additional purification. The general procedure
of conducting the experiments has been reported earlier.31 In
the present study, two methods for the introduction of the cataꢀ
lyst were employed. According to one of them, MAO (~3/4 of
the calculated amount of a 10% solution in toluene) was feeded
to the reactor with liquid propylene. The mixture was stirred and
then the tested complex dissolved in a solution of the rest of
MAO was added. Alternatively, solid complex was introduced
into the reactor following loading the calculated amount
of MAO.
The 13C NMR spectra of PP in 1,1,2,2ꢀtetrachloroethaneꢀd2
(7.5% wt/wt) were recorded on a Bruker АСꢀ200 instrument
at 110 °С. The Xꢀray diffraction analysis of PP specimens was
carried out on a DRONꢀ2 diffractometer. Mechanical tests were
performed on a tensileꢀtesting machine Instronꢀ1122 according
to a known procedure.32
17. C. Dijkgraff and J. Rousseau, J. Am. Chem. Soc., 1990,
112, 3952.
18. T. Matsugi, S. Matsui, S. Kojoh, Y. Takagi, I. Inoue,
T. Nakano, T. Fujita, and N. Kashiwa, Macromolecules,
2002, 35, 4880; Y. Yoshida, S. Matsui, Y. Takagi, M. Mitani,
T. Nakano, H. Tanaka, N. Kashiwa, and T. Fujita, Organoꢀ
metallics, 2001, 20, 4793.
19. S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio,
N. Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru,
T. Nakano, H. Tanaka, N. Kashiwa, and T. Fujita, J. Am.
Chem. Soc., 2001, 123, 6847.
20. E. Y.ꢀX. Chen and T. J. Marks, Chem. Rev., 2000, 100, 1391.
21. S. Ch. Gagieva, T. A. Sukhova, D. V. Savinov, V. A. Optov,
N. M. Bravaya, Yu. N. Belokon´, and B. M. Bulychev, Izv.
Akad. Nauk, Ser. Khim., 2003, 1605 [Russ. Chem. Bull., Int.
Ed., 2003, 52, 1693].
22. S. C. Gagieva, T. A. Sukhova, D. V. Savinov, V. A. Optov,
N. M. Bravaya, Y. N. Belokon´, and B. M. Bulychev,
J. Polym. Sci. A: Polym. Chem., 2005, 95, 1040.
23. A. I. Tarutina and F. O. Pozdnyakova, Spektral'nyi analiz
polimerov [Spectral Analysis of Polymers], Khimiya,
Leningrad, 1986, 248 pp. (in Russian).
Molecularꢀmass characteristics (Mw, Mn, Mw/Mn) of PE
and PP were determined by gel permeation chromatography on
a Waters 150ꢀC instrument equipped with a linear column with
HTꢀµꢀStyragel in using solutions of the polymers in 1,2ꢀdichloꢀ
robenzene at 135 °C.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 06ꢀ03ꢀ
33038ꢀа and 05ꢀ03ꢀ32771ꢀа).
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Received June 2, 2005;
in revised form October 17, 2006