Supporting Information for:
Imino-indolide Half-Titanocene Chlorides: Synthesis and Their
Ethylene (Co)polymerization
WEIWEI ZUO, MIN ZHANG, WEN-HUA SUN
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular
Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
1.
13C
NMR spectrum of poly(ethylene-co-1-hexene) prepared by C1/MAO
catalytic system
Figure S1. 13C NMR spectrum of poly(ethylene-co-1-hexene) prepared by C1/MAO
catalytic system (entry1, Table 5).
The micro-structures of the poly(ethylene-co-1-hexene)s obtained were characterized by
13
C NMR techniques. The
13
C NMR spectrum of the copolymer obtained using 0.3
mol/l 1-hexene and 1 atm of ethylene pressure (entry1, Table 5) is shown in Figure S1,
and is similar to the spectra of LLDPE.1 There is a strong resonance at δ = 30.0 ppm

Corresponding author Tel: 86-10-62557955, Fax: 86-10-62618239, E-mail address: whsun@iccas.ac.cn
attributable to ethylene units and a number of weaker but nonetheless distinct
resonances attributed to the butyl branches of 1-hexene-copolymerized sequences. The
content of 1-hexene is 1.01 mol% according to the reported determination methods.2
The assignments were determined according to the literature procedures,2, 3 following
the nomenclature of Usami and Takayama.4
2. 1H NMR spectrum of poly(ethylene-co-methyl 10-undecenoate) prepared by
C1/MAO catalytic system
Figure S2. 1H NMR spectrum of poly(ethylene-co-methyl 10-undecenoate) prepared by
C1/MAO catalytic system (Table 6, entry 1).
In addition to the major chemical shift at 1.5ppm, which corresponds to CH2 groups in
both ethylene and methyl 10-undecenoate units, the spectrum also shows a resonance at
3.76 ppm, which represents the characteristic resonance for the methyl ester group in
the incorporated methyl 10-undecenoate unit. Using the methyl ester group as calibrant
and deducting the corresponding methylene and methyne protons that methyl
10-undecenoate is expected to contribute to the peaks around 1.5ppm, the ratio of
ethylene and methyl 10-undecenoate units in the copolymer was estimated. It was found
that the copolymer sample incorporates an estimated 1.02 mol% of methyl
10-undecenoate unit.5
3. DSC curve of poly(ethylene-co-methyl 10-undecenoate) prepared by C1/MAO
catalytic system
Figure S3. DSC curve of poly(ethylene-co-methyl 10-undecenoate) prepared by
C1/MAO catalytic system (Table 6, entry 1).
4. FT-IR spectrum of poly(ethylene-co-methyl 10-undecenoate) prepared by
C1/MAO catalytic system
Figure S4. FT-IR spectrum of poly(ethylene-co-methyl 10-undecenoate) prepared by
C1/MAO catalytic system: the methyl 10-undecenoate was pretreated by Et2AlCl prior
to polymerization (Table 6, entry 5).
5.
Ethylene/methyl
bis(imino-indolide)titanium
10-undecenoate
copolymerization
dichlorides6
bis(2-(6-methylpyridin-2-yl)-benzimidazolyl)titanium dichlorides7
using
and
cat/MAO
(CH2)8COOMe
x
Al compounds
1-x
(CH2)8
C O
Cl
OMe
N
cat:
N
Ti
N
Cl
Cl
N
N
N
Cl
Ti Cl
N
N
N
Cl
N
bis(imino-indolide)titanium dichlorides
bis(2-(6-methylpyridin-2-yl)-benzimidazolyl)titanium dichlorides
Al compounds: MAO, Et2AlCl
Scheme S1
To get more information of the effect of Et2AlCl, copolymerizations were also carried
out
by
using
bis(imino-indolide)titanium
bis(2-(6-methylpyridin-2-yl)-benzimidazolyl)titanium
dichlorides6
dichlorides7
as
and
precatalysts,
which were also synthesized in our lab. For comparison, in each catalytic system the
methyl 10-undecenoate was pretreated with Et2AlCl and MAO, respectively (Scheme
S1). The other polymerization parameters were similar to those of entry 1–6 of Table 6
in the main text. In the case of bis(imino-indolide) titanium dichloride/MAO
polymerization system, when the comonomer was pretreated with Et2AlCl, polymeric
samples were obtained with a heterogeneous composition (Figure S5a), analogously to
what occurred in the polymerization with C1/MAO in the presence of Et2AlCl.
However, for methyl 10-undecenoate pretreated by MAO, its copolymerization with
ethylene using the same catalyst yield copolymers with homogeneous composition, as
revealed
by
DSC
analysis
(Figure
S5b).
On
the
contrary,
when
bis(2-(6-methylpyridin-2-yl)-benzimidazolyl)titanium dichloride was used as catalyst,
using both Et2AlCl and MAO as pretreatment reagent, homogeneous polymers were
obtained in both cases (Figure S6a and b). From the above phenomena, it can be
suggested that when Et2AlCl was employed as pretreatment reagent, catalyst that bears
imine groups in the ligand produces heterogeneous polymers, while catalyst that do not
contain imine ligands led to homogeneous polymers.
a
b
Figure S5. DSC curves of poly(ethylene-co-methyl 10-undecenoate)s prepared by
bis(imino-indolide) titanium dichloride/MAO catalytic system: (a) the methyl
10-undecenoate was pretreated by Et2AlCl prior to polymerization; (b) the methyl
10-undecenoate was pretreated by MAO prior to polymerization.
a
b
Figure S6. DSC curves of poly(ethylene-co-methyl 10-undecenoate)s prepared by
bis(2-(6-methylpyridin-2-yl)-benzimidazolyl)titanium dichloride/MAO catalytic system:
(a) the methyl 10-undecenoate was pretreated by Et2AlCl prior to polymerization; (b)
the methyl 10-undecenoate was pretreated by MAO prior to polymerization.
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