Copolymerization of ethylene with 1,1-disubstituted olefins catalyzed by ansa-(fluorenyl)(cyclododecylamido)dimethyltitanium complexes

Article abstract of DOI:10.1002/pola.26491

A series of titanium complexes with ansa-(fluorenyl)(cyclododecylamido) ligands, Me₂Si(η³-R)(N-c-C₁₂H ₂₃)TiMe₂ [R = fluorenyl (5), 2,7-^tBu ₂fluorenyl (6), 3,6-^tBu₂fluorenyl (7)], was synthesized. The crystal structure of complex 6 revealed η³- coordination of the fluorenyl moiety to the metal. Upon activation with trialkylaluminum-free modified methylaluminoxane, complexes 5-7 as well as the corresponding ^tBu amide complexes, Me₂Si(η ³-R)(N^tBu)TiMe₂ [R = fluorenyl (2), 2,7- ^tBu₂fluorenyl (3), 3,6-^tBu₂fluorenyl (4)], were adopted as the catalysts for the copolymerization of ethylene (E) and isobutylene (IB). Among these complexes, complex 6 was found to achieve the highest IB incorporation to produce alternating E-IB copolymers. Complex 6 system also achieved copolymerization of E and limonene. 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013. Copyright

Full text of DOI:10.1002/pola.26491

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
Copolymerization of Ethylene with 1,1-Disubstituted Olefins Catalyzed by
ansa-(Fluorenyl)(cyclododecylamido)dimethyltitanium Complexes
Yuushou Nakayama, Yuuichi Sogo, Zhengguo Cai, Takeshi Shiono
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
Correspondence to: T. Shiono (E-mail: tshiono@hiroshima-u.ac.jp)
Received 30 July 2012; accepted 15 November 2012; published online 18 December 2012
DOI: 10.1002/pola.26491
ABSTRACT: A series of titanium complexes with ansa-(fluore-
lysts for the copolymerization of ethylene (E) and isobutylene
(IB). Among these complexes, complex 6 was found to achieve
the highest IB incorporation to produce alternating E-IB copoly-
mers. Complex 6 system also achieved copolymerization of E
and limonene. VC 2012 Wiley Periodicals, Inc. J. Polym. Sci.,
3
nyl)(cyclododecylamido) ligands, Me
2
Si(g -R)(N-c-C12
H
23)TiMe
2
t
t
2 2
[
R ¼ fluorenyl (5), 2,7- Bu
fluorenyl (6), 3,6- Bu fluorenyl (7)],
was synthesized. The crystal structure of complex 6 revealed
3
g -coordination of the fluorenyl moiety to the metal. Upon acti-
vation with trialkylaluminum-free modified methylaluminox-
Part A: Polym. Chem. 2013, 51, 1223–1229
t
ane, complexes 5–7 as well as the corresponding Bu amide
3
t
t
complexes, Me
2
Si(g -R)(N Bu)TiMe
2
[R ¼ fluorenyl (2), 2,7- Bu2-
KEYWORDS: alternating copolymerization; ethylene; isobutylene;
t
fluorenyl (3), 3,6- Bu
2
fluorenyl (4)], were adopted as the cata-
limonene; metallocene catalysts; modified methylaluminoxane
INTRODUCTION ansa-Cyclopentadienyl-amido complexes of
titanium developed by Dow and Exxon have been known as
constrained geometry catalysts (CGCs), which show excellent
Conversely, we have been studying the fluorenyl analogues
3
t
of CGCs, Me
2,7- Bu fluorenyl (3), 3,6- Bu fluorenyl (4)] (Scheme 1),
2
Si(g -R)(N Bu)TiMe
2
[R
¼
fluorenyl (2),
t
t
2 2
7–9
1,2
10
performance for the copolymerization of olefin monomers.
as catalysts for olefin polymerization. These complexes 2–4
In comparison with bis(cyclopentadienyl) type complexes,
the CGCs have wide coordination site for olefin polymeriza-
tion, which allows easier access of bulky monomers to the
were found to be highly effective catalysts for homo- and
11
co-polymerization of higher a-olefins
and cyclic olefins
12–20
such as norbornene.
We assumed that the combination
catalyst metal center. A representative form of the CGCs,
of cyclododecylamido and fluorenyl groups for titanium com-
plexes should be useful to develop more effective catalysts
for the polymerization of bulky 1,1-disubstituted olefins.
t
Me
2
Si(C
5
Me
4
)(N Bu)TiMe
2
(CGC), is shown in Scheme 1.
Among the olefin monomers, the polymerization of 1,1-dis-
ubstituted olefins such as isobutylene (IB) has been less
explored in comparison with those of ethylene and a-
In this study, a series of titanium complexes with ansa-(fluo-
3
renyl)(cyclododecylamido) ligands, Me
Si(g -R)(N-c-C12
H
)
2
23
3
–6
t
t
2 2
olefns.
The copolymerization of ethylene (E) with IB by
TiMe
2
[R ¼ fluorenyl (5), 2,7- Bu
fluorenyl (6), 3,6- Bu fluor-
ansa-metallocene type complexes were reported to give low
enyl (7)] (Scheme 1), was synthesized and used as catalyst
precursors for E-IB copolymerization. The copolymerization
of ethylene with a plant-derived 1,1-disubstituted olefin,
d-limonene (LM), was also performed by this catalyst system.
molecular weight copolymers with low IB-content (<3 mol
4
%
). Shaffer and coworkers have reported an outstanding
example of E-IB copolymerization by an ansa-cyclopenta-
dienyl-cyclododecylamido complex of titanium, Me Si(C5-
2
RESULTS AND DISCUSSION
Me )(N-c-C H )TiMe (1), in which alternating copolymer
4
12 23
2
of E and IB (IB content ꢀ45%) was produced under high IB
Synthesis of the Titanium Complexes
The titanium complexes 5–7 were synthesized in the similar
procedure for the synthesis of 2–4 (Scheme 2). The molec-
ular structure of 6 was determined by X-ray crystallography
(Fig. 1). Although the quality of the crystal was not very
good, the Ti–C(fluorenyl) distances in 6 were similar to
5
concentration. Marks and coworkers reported a pair of
8,9
binuclear catalyst precursor and activator was effective for
E-IB copolymerization to give copolymers with relatively
high IB-content (ꢀ15.2%) in comparison with those in the
6
corresponding mononulcear systems.
*Present address: Zhengguo Cai, State Key Lab of Chemical Fibers & Polymer Materials, College of Material Science &
Engineering, Donghua University, Shanghai 201620, China.
V
C
2012 Wiley Periodicals, Inc.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229
1223

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
SCHEME 1 Titanium complexes as catalyst precursors for olefin polymerization.
those in complexes 2–4, in which the fluorenyl moiety coor-
dinates to the titanium in g -coordination mode (Table 1).
1 afforded a E-IB copolymer with IB content of 45 mol %
3
10
under high IB concentration (6.3 mol/L) and low E pres-
5
sure (0.34 atm). The use of complex 6 achieved higher
Copolymerization of Ethylene and IB
IB-content (48 mol %) even under significantly lower IB
concentration (1.78 mol/L) and higher E pressure (1 atm)
conditions.
The catalytic activity of complexes 2–7 and CGC for E-IB
copolymerization was studied in toluene at room tempera-
ture under atmospheric pressure of ethylene with 3.0 g of
IB in 30 mL of toluene (Table 2). In this study, trialkylalu-
minum-free modified methylaluminoxane (dMMAO) was
chosen as an activator because the 2–4/dMMAO systems
have been found to promote living polymerization of a-ole-
13
In the C NMR spectrum of the copolymer obtained by com-
plex 6 (Fig. 2), the strong signals assignable to a, b, bb, and
ac protons were observed, while no signals assignable to IB-
IB sequence appeared. Together with high IB-content (48%),
the E-IB copolymer obtained with 6 can be regarded as an
alternating E-IB copolymer.
9
,21
fins,
although the present E-IB copolymerization did not
proceed in a living fashion (vide infra). In comparison with
the corresponding tert-butylamido complexes 2–4 (runs
Using complex 6, the E-IB copolymerizations were performed
under different conditions (Table 3). The IB-contents of the
resulting copolymers increased with increasing feed IB to
reach 49 mol % (run 8), but did not exceed 50 mol %, in ac-
1
–3), the cyclododecylamido complexes 5–7 (runs 4–6)
showed similar activity and produced E-IB copolymers with
somewhat lower molecular weights, similar molecular
weight distributions, and apparently higher IB-contents
13
cordance with the absence of IB-IB sequence in the C NMR
spectra. With increasing feed IB, the activity reached maxi-
mum at 2.0 g and then decreased, while the molecular
weight of the resulting copolymers monotonously decreased
with the increase of feed IB amount.
(
5
35–48 mol %). Among the cyclododecylamido complexes
–7, the 2,7-di-tert-butylfluorenyl complex 6 produced the
E-IB copolymer with the highest IB-content (run 5, 48 mol
). The reported E-IB copolymerization by complex
%
SCHEME 2 Synthesis of titanium complexes 5–7.
1
224
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
TABLE 2 Copolymerization of Ethylene with Isobutylene by
a
Various Complexes
d
IB-Content
(mol %)
b
4c
c
Run Catalyst Activity
M
n
ꢄ 10
w Mn
M /
1
2
3
4
5
6
7
a
2
143
349
272
246
257
318
58
2.1
5.9
6.9
1.8
3.2
2.7
1.9
1.8
2.0
2.8
1.9
1.7
1.9
2.0
18
17
10
35
48
38
3
3
4
5
6
7
CGC
Polymerization conditions: Ti ¼ 20 lmol, Al/Ti ¼ 400, solvent ¼ tolu-
ene, total volume ¼ 30 ml, cocatalyst ¼ dMMAO, E/IB (mol/mol) ¼ 0.18,
ꢂ
E ¼ 0.32 mol/l (1 atm), IB ¼ 3 g (1.78 mol/l), temp ¼ 25 C, time ¼ 5
min.
b
ꢁ1 ꢁ1
h .
Activity ¼ kg(poly) mol(Ti)
Number-average molecular weight and molecular weight distribution
c
determined by GPC using polystyrene standard.
FIGURE 1 ORTEP drawing of complex 6.
d
13
5,6
Determined by C NMR.
ꢂ
Copolymerization of Ethylene and Limonene
The observed T values (ꢁ29 to ꢁ22 C) were much higher
g
ꢂ
5
LM is one of the plant-derived 1,1-disubstituted olefins. We
also studied the copolymerization of E with LM to develop a
novel partially biomass-based polymer. Complex 6 was
adopted for the E-LM copolymerization because it was the
most effective for E-IB copolymerization among the com-
plexes used in this study. We speculated that such a bulky
disubstituted olefin like LM should be difficult to be poly-
merized, so the E-LM copolymerization with 6 was per-
formed overnight. The results are summarized in Table 4.
Compared with ethylene homopolymerization (run 14) and
E-IB copolymerization (Table 3), E-LM copolymerization
actually proceeded much slower.
than those of homopolyeththylene (ꢁ80 C) and homopolyi-
ꢂ
5
sobutylene (ꢁ73 C) because of their alternating nature, as
5
reported by Shaffer et al. To the best of our knowledge, the
ꢂ
T value of ꢁ22 C for the E-IB copolymer (IB content 49
g
mol %, run 12) is the highest among those of the so far
5
reported E-IB copolymers. The differential scanning calo-
rimetry (DSC) analysis of those E-IB copolymers showed
small melting peak (e.g., DH
m
¼ 0.7 J/g for run 8), possibly
due to small amounts of byproducts such as homopolyethy-
lene and/or copolymers with high E-contents, suggesting the
formation of some different active species with low IB-incor-
2
2
poration ability.
The E-IB copolymerization in chlorobenzene by complex 6
run 11) was similar to that in toluene (run 5), while that in
heptane (run 12) resulted in decrease of IB-content of the
resulting copolymer. The use of MMAO instead of dMMAO
was found to reduce catalytic activity as well as the molecu-
lar weight and the IB-content of the obtained copolymer
1
Figure 3 shows the H NMR spectrum of the E-LM copoly-
mer obtained in run 16. Because the obtained copolymers in
runs 15 and 16 were completely soluble in o-dichloroben-
(
sene and tetrachloroethane-d , we assumed that the internal
2
double bond of LM had been remained unreacted. Thus, the
LM-contents of the copolymers were calculated by the fol-
lowing equation:
(
run 13), possibly due to adduct formation of cationic tita-
nium active species with trialkylalumium. Homopolymeriza-
tion of IB did not proceed by this catalyst system as
expected (run 14).
LM-content ðmol %Þ ¼ ½A5:1=fA5:1
þ ðA0:7ꢁ2:4 ꢁ 15A5:1Þ=4gꢃ ꢄ 100
where A5.1 and A0.7–2.4 are the area of the peaks at 5.1 and
˚
0.7–2.4 ppm, respectively. Although the peaks have not been
TABLE 1 Comparison of Interatomic Distances (A) of the Ti
13
Complexes
fully assigned, C NMR spectra of the obtained copolymers
also supported incorporation of the LM unit (Fig. 4). Under
similar conditions with those in the E-IB copolymerization
except for polymerization time (run 15), complex 6 produced
E-LM copolymer with LM-content of approximately 1 mol %.
Reduction of feed ethylene monomer resulted in the produc-
tion of E-LM copolymer with LM-content of approximately 4
mol %, lower molecular weight, and broader molecular
weight distribution (run 16). Homopolymerization of LM did
not proceed by the present catalyst system of 6 (run17).
1
0
10
10
10
2
3
4
CGC
6
TiAC9
2.252(3)
2.415(3)
2.572(3)
2.573(3)
2.418(3)
1.923(3)
2.236(2)
2.470(2)
2.663(2)
2.620(2)
2.366(3)
1.917(3)
2.247(3)
2.422(3)
2.619(3)
2.609(3)
2.401(3)
1.923(3)
2.283(3)
2.350(3)
2.463(3)
2.463(3)
2.350(3)
1.947(4)
2.297(7)
2.407(7)
2.546(8)
2.586(7)
2.443(7)
1.908(6)
TiAC10
TiAC11
TiAC12
TiAC13
TiAN
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229
1225

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
1
3
2
FIGURE 2 C NMR spectrum (tetrachloroethane-d ) of the obtained poly(ethylene-co-isobutylene) (Table 2, run 5).
The DSC analysis of the produced E-LM copolymers showed
apparently lower T and DH (runs 15 and 16) in comparison
with those of homopolyethylene (run 14), which also sup-
ported the formation of E-LM copolymers. To the best of our
knowledge, this is the first example of E-LM copolymerization.
atmosphere of pure and dry nitrogen, using standard
Schlenk techniques. NMR spectra were measured on a Varian
system500 (500 MHz) spectrometer and a Lambda500 (500
MHz) spectrometer. Molecular weight and molecular weight
m
m
distribution of the obtained polymers were determined by
ꢂ
gel permeation chromatography with a PL 210 at 140
C
CONCLUSIONS
using o-dichlorobenzene as a solvent. The parameters for
ꢁ
4
universal calibration were K ¼ 1.38 ꢄ 10 , a ¼ 0.7 for
polystyrene standard. DSC analyses were performed on a
Seiko DSC-6220 apparatus under a nitrogen atmosphere
with several heating rate.
In conclusion, we demonstrated that ansa-(fluorenyl)(cyclo-
dodecylamido) complexes of titanium are effective for the
copolymerization of ethylene with 1,1-disubstituted olefins
such as IB and LM. Among the used complexes in this study,
the complex 6 was the most effective for E-IB copolymeriza-
tion and produced E-IB alternating copolymers. The complex
Materials
n-Hexane and tetrahydrofuran from Kanto Chemical Co. were
deaerated under vacuum and were dried with activated mo-
lecular sieves 4A. Dehydrated diethyl ether was purchased
from Kanto Chemical Co. and used without further purifica-
tion. Dibenzocyclopentadiene (fluorene), 2,7-di-tert-butyl-
fluorene, 3,6-di-tert-butylfluorene, dichlorodimethylsilane,
cyclododecylamine, titanium tetrachloride, n-butyllitium,
methyllitium, and methylmagnesium bromide, were used as
6
also promoted the E-LM copolymerization to give E-LM
copolymers with LM-content of ꢀ4 mol %.
EXPERIMENTAL
General Remarks
Because of air and moisture sensitivity of organometallic
compounds, all the manipulations were carried out under an
1
226
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
a
TABLE 3 Copolymerization of Ethylene and Isobutylene with 6
b
4c
c
d
e
ꢂ
e
m
ꢂ
e
m
Run
IB (g)
Activity
M
n
ꢄ 10
M
w
/M
n
IB-Content (mol %)
T
g
( C)
T
( C)
DH
(J/g)
8
5
9
6.1
3.0
2.0
1.5
3.0
3.0
3.0
3.0
150
257
610
460
315
282
23
0.9
3.2
3.4
4.8
1.2
2.3
0.8
–
1.9
1.7
2.0
1.8
2.3
2.4
3.6
–
49
48
43
37
47
37
35
–
ꢁ22
ꢁ23
ꢁ25
123
128
128
129
n.d.
n.d.
n.d.
–
0.7
0.7
6.9
7.8
10
11
12
13
14
a
ꢁ29g
f
g
g
g
g
n.d.
n.d.
n.d.
n.d.
–
h
i
g
g
g
n.d.
g
n.d.
j
Trace
–
e
Polymerization conditions: catalyst ¼ 6, Ti ¼ 20 lmol, Al/Ti ¼ 400, sol-
Ditermined by DSC.
Solvent ¼ chlorobenzene.
Not determined.
f
vent ¼ toluene, total volume ¼ 30 mL, cocatalyst ¼ dMMAO, E ¼ 0.32
ꢂ
g
h
i
mol/l (1 atm), temp. ¼ 25 C, time ¼ 5 min.
b
c
ꢁ1 ꢁ1
h .
Activity ¼ kg(poly) mol(Ti)
Solvent ¼ heptane.
Cocatalyst ¼ MMAO.
Number-average molecular weight and molecular weight distribution
j
determined by GPC using polystyrene standard.
d
Homopolymerization of isobutylene.
13
5,6
Determined by C NMR.
purchased. Toluene and heptane were refluxed and distilled
over sodium/benzophenone. MMAO solution in toluene was
supplied by Tosoh Finechem Co. Dried modified methylalmi-
noxane(dMMAO) was prepared by evaporation of the MMAO
solution in toluene, followed by repeated redissolving in hep-
1H, C H ), 1.2–1,4 (brs, 22H, C H ), 1.09 (brs, 1H, NH),
12 23 12 23
ꢁ0.03 (s, 6H, SiCH3).
3
2 2
Synthesis of Me Si(g -fluorenyl)(N-c-C12H23)TiMe (5)
MeLi solution (1.09 M, 21.0 ml, 21.4 mmol) in diethyl ether
2
1
ꢂ
tane and evaporation. LM was used as purchased. The com-
was dropwise added at 0 C to a solution of Me
Si(fluore-
2
8
,9
23
plexes 2–4
and CGC
were synthesized according to
nyl)(NH-c-C12H23) (2.1 g, 5.1 mmol) in diethyl ether (30 ml),
iterature.
and the mixture was stirred for 3 h at r.t. The mixture was
added to a solution of TiCl (0.56 mL, 5.1 mmol), in hexane
4
(
15 mL). After stirring the suspension at r.t. overnight, the
Synthesis of Me
n-BuLi solution (1.59 M, 8.18 ml, 13.0 mmol) in hexane was
dropwise added at 0 C to a solution of cyclododecylamine
2
Si(fluorenyl)(NH-c-C12
H
23
)
solvent was removed in vacuo and the residue was extracted
with hexane (60 mL). Then, 3 M MeMgBr (4.3 mL, 12.8
mmol) was added to the solution at r.t. and was stirred for
1 h. The solvent was removed in vacuo and the residue was
extracted with hexane (60 mL). Then, the hexane solution
ꢂ
(
1.9 g, 10 mmol) in diethyl ether (30 ml), and the mixture
was stirred for 3 h at r.t. The resulting lithium salt was sus-
pended in diethyl ether (30 ml), and added to a solution of
ꢂ
3
was concentrated and cooled to ꢁ30 C to give Me Si(g -flu-
2
2
4
9
-(ClSiMe )fluorene (2.9 g, 11.2 mmol) in diethyl ether (30
orenyl)(N-c-C H )TiMe (5) as a red powder.
2
ꢂ
12 23
2
ml) at 0 C. After the mixture was stirred for 1 h at r.t., all
the volatiles were removed in vacuo and the residue was
extracted with hexane. The extract was evaporated in vacuo
to give Me Si(fluorenyl)(NH-c-C H ) as a yellow solid (2.83
1
H NMR (C
6
D
6
: 7.16 ppm): d ¼ 7.82 (d, 2H, Flu), 7.60 (d, 2H,
Flu), 7.27–7.32 (m, 4H, Flu), 2.59 (m, 1H, C H ), 1.1–1.5 (brs,
12 23
2
2H, C H ), 0.16 (s, 6H, SiCH ), and 0.03 (s, 6H, TiCH ).
12 23 3 3
2
12 23
g, 7.0 mmol, 63%).
t
Synthesis of Me Si(2,7- Bu fluorenyl)(NH-c-C12H23
)
2
2
1
t
H NMR (CDCl : 7.26 ppm): d ¼ 7.85 (d, 2H, Flu), 7.58 (d,
Me Si(2,7- Bu fluorenyl)(NH-c-C H ) was synthesized in a
2 2 12 23
similar manner for Me Si(fluorenyl)(NH-c-C H ) using
2 12 23
3
2H, Flu), 7.25–7.35 (m, 4H, Flu), 3.82 (s,1H, Flu), 2.66 (m,
a
TABLE 4 Copolymerization of Ethylene and Limonene with 6.
Amount of Ethylene
b
b
c
d
m
d
Run
Limonene
Gas Dissolved
Temp.
Yield
M
n
M
w
/M
n
LM-Content
T
DH
m
e
1
1
1
1
a
4
5
6
7
0
350
276
70
25
25
25
25
0.47
0.16
0.11
Trace
c
5.5
5.7
0.8
–
2.6
1.5
23.8
–
–
133.7
126.2
123.8
–
121.0
34.1
4.4
53.5
53.5
53.5
1.1
3.9
–
f
0
–
Polymerization conditions: Ti ¼ 20 lmol, Al/Ti ¼ 400, solvent ¼ tolu-
Determined by 1H NMR.
Determined by DSC.
d
e
ene, total volume ¼ 30 ml, catalyst ¼ 6, d-limonene ¼ 7.3 g, cocatalyst
ꢂ
ꢁ1
¼
dMMAO, E ¼ 0.32 mol/l (1 atm), temp ¼ 25 C, time ¼ overnight.
Ethylene homopolymeriztion: time ¼ 5 min, activity ¼ 282 kgꢅmol(Ti)
b
ꢁ1
Number-average molecular weight and molecular weight distribution
h
f
.
determined by GPC using polystyrene standard.
Limonene homopolymerization.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229
1227

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
1
FIGURE 3 H NMR spectrum (tetrachloroethane-d
2
) of the obtained poly(ethylene-co-limonene) (Table 3, run 16).
t
9,25
2
,7- Bu
2
-9-ClSiMe
2
-fluorene
instead of 9-ClSiMe
2
-fluorene
(t, 6H, Et
0.03 (s, 6H, TiCH
2
O), 0.21 (s, 3H, SiCH
).
3 3
), 0.07 (s, 3H, SiCH ), and
and obtained as a yellow oil in 93% yield.
3
1
t
H NMR (CDCl
3
: 7.26 ppm): d ¼ 7.70 (d, 2H, Flu), 7.59 (s,
Synthesis of Me Si(3,6- Bu fluorenyl)(NH-c-C12H23
)
2
2
t
2
H, Flu), 7.34 (d, 2H, Flu), 3.77 (s,1H, Flu), 2.66 (m, 1H,
Me Si(3,6- Bu fluorenyl)(NH-c-C H ) was synthesized in a
similar manner for Me Si(fluorenyl)(NH-c-C H ) by using
2
3,6- Bu -9-ClSiMe -fluorene
2
2
12 23
t
C H ), 1.2–1,5 (brs, 22H, C H ), 1.38 (s, 18H, Bu), 1.10
1
2
23
12 23
12 23
t
9,25
(
brs, 1H, NH), ꢁ0.03 (s, 6H, SiCH3).
2
2
instead of 9-ClSiMe -fluorene
2
and obtained as a yellow oil in 90% yield.
3
t
Synthesis of Me Si(g -2,7- Bu fluorenyl)
2
2
1
H NMR (CDCl : 7.26 ppm): d ¼ 7.85 (s, 2H, Flu), 7.47 (d,
(
N-c-C12H23)TiMe (6)
Me Si(g -2,7- Bu fluorenyl)(N-c-C H )TiMe (6) was syn-
thesized in a similar manner for complex 5 using Me
Bu fluorenyl)(NH-c-C12 23) instead of Me Si(fluorenyl)(NH-
c-C H ) and obtained as red crystals.
3
2
3
t
2
H, Flu), 7.30 (d, 2H, Flu), 3.70 (s,1H, Flu), 2.64 (m, 1H,
2
2
12 23
2
t
t-
C H ), 1.41 (s, 18H, Bu), 1.2–1,4 (brs, 22H, C H ), 1.18
2
Si(2,7-
12 23
12 23
(
m, 1H, NH), and 0.00 (s, 6H, SiCH3).
2
H
2
1
2 23
3
t
2 2
Synthesis of Me Si(g -2,7- Bu fluorenyl)
1
H NMR (CDCl : 7.26 ppm): d ¼ 7.69 (d, 2H, Flu), 7.58 (s,
(N-c-C12H23)TiMe (7)
2
3
3
t
2
H, Flu), 7.33 (d, 2H, Flu), 3.48 (q, 4H, Et O), 2.66 (m, 1H,
Me Si(g -3,6- Bu fluorenyl)(N-c-C H )TiMe
2
(7)
was
2
2
2
12 23
t
C H ), 1.2–1.5 (brs, 22H, C H ), 1.38 (s, 18H, Bu), 1.21
synthesized in a similar manner for complex 5 using
1
2
23
12 23
1
3
2
FIGURE 4 C NMR spectrum (tetrachloroethane-d ) of the obtained poly(ethylene-co-limonene) (Table 3, run 16).
1
228
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
t
Me Si(3,6- Bu fluorenyl)(NH-c-C H ) instead of Me Si
ACKNOWLEDGMENTS
2
2
12 23
2
(
fluorenyl)(NH-c-C12
H
23) and obtained as yellow crystals.
This work was financially supported by Advanced Low Carbon
Technology Research and Development Program from Japan
Science and Technology Agency.
1
H NMR (C
6
D
6
: 7.16 ppm): d ¼ 8.20 (s, 2H, Flu), 7.63 (d, 2H,
O), 2.65 (m, 1H,
Flu), 7.42 (d, 2H, Flu), 3.26 (q, 6H, Et
C H ), 1.40 (s, 9H, Bu), 1.38 (s, 9H, Bu), 1.2–1.4 (brs,
2
t
t
1
2 23
22H, C H ), 1.12 (t, 6H, Et O), 0.16 (s, 3H, SiCH ), 0.13 (s,
12 23 2 3
3
H, SiCH ), and ꢁ0.14 (s, 6H, TiCH ).
3
3
REFERENCES AND NOTES
1
McKnight, A. L., R. M. Waymouth, Chem. Rev. 1998, 98,
Procedure for the Copolymerization of Ethylene with IB
Polymerization was performed in a 100 mL glass reactor
equipped with a magnetic stirrer. The reactor was charged
with a prescribed amount of dMMAO, followed by introduc-
tion of ethylene gas (1 atm). After adding toluene and a pre-
scribed amount of IB, the reactor was kept stirring until the
solvent was saturated with ethylene gas. Polymerization was
started by successive addition of 1 mL solution of catalyst
2
587–2598.
2
2
H. Braunschweiga, F. M. Breitling, Coord. Chem. Rev. 2006,
50, 2691–2720.
3
P. Pino, U. Giannini, Porri, L. In Encyclopedia of Polymer Sci-
ence and Engineering, 2nd ed.; H. F. Mark, N. M. Bikales, C. C.
Overberger, G. Menges, Eds.; Wiley: New York, 1987, p 175.
4 W. Kaminsky, H. Sinn, Transition Metals and Organometallics
as Catalysts for Olefin Polymerization; Springer: Berlin, 1988.
(
20 lmol) and conducted for a given time, and then termi-
5 T. D. Shaffer, J. A. M. Canich, K. R. Squire, Macromolecules
1998, 31, 5145–5147.
nated with acidic methanol. The obtained polymers were
adequately washed with methanol and dried under vacuum
at 60 C for 6 h.
6 H. Li, L. Li, T. J. Marks, L. Liable-Sands, A. L. Rheingold, J.
Am. Chem. Soc. 2003, 125, 10788–10789.
ꢂ
7
H. Hagihara, T. Shiono, T. Ikeda, Macromolecules 1998, 31,
3
184–3188.
Procedure for the Copolymerization of Ethylene with LM
Polymerization was performed in a 100 mL glass reactor
equipped with a magnetic stirrer. The reactor was added sol-
vent, followed by charge a prescribed amount of dMMAO
and an appropriate amount of ethylene gas and LM. Poly-
merization was started by successive addition of 1 mL solu-
tion of catalyst (20 lmol). The polymerization was con-
ducted for a given time, and then terminated with acidic
methanol. The obtained polymers were adequately washed
8
K. Nishii, H. Hagihara, T. Ikeda, M. Akita, T. Shiono, J. Orga-
nomet. Chem. 2006, 691, 193–201.
9
3
Z. Cai, T. Ikeda, M. Akita, T. Shiono, Macromolecules 2005,
8, 8135–8139.
1
0 T. Shiono, Polym. J. 2011, 43, 331–351.
1
1 Z. Cai, M. Ohmagari, Y. Nakayama, T. Shiono, Macromol.
Rapid Commun. 2009, 30, 1812–1816.
1
2 T. Hasan, K. Nishii, T. Shiono, T. Ikeda, Macromolecules
2002, 35, 8933–8935.
ꢂ
with methanol and dried under vacuum at 60 C for 6 h.
13 T. Hasan, T. Ikeda, T. Shiono, Macromol. Symp. 2004, 213,
1
23–129.
1
8
4 T. Hasan, T. Ikeda, T. Shiono, Macromolecules 2004, 37,
503–8509.
Crystallographic Study of Complex 6
A single crystal of complex 6 sealed in a glass capillary
under argon was mounted on a Rigaku RAXIS RAPID Imag-
ing Plate diffractometer with MoKa radiation at 123 K.
Indexing was performed three oscillations, which were
exposed for 3.0 min. The camera radius was 127.40 mm.
Readout was performed in the 0.10 mm pixel mode. The
data were corrected for Lorentz and polarization effects.
The structure was solved by direct method and refined by
1
7
5 T. Hasan, T. Ikeda, T. Shiono, Macromolecules 2004, 37,
432–7436.
1
1
6 T. Hasan, T. Ikeda, Shiono, T. Macromolecules 2005, 38,
071–1074.
1
2
7 Z. Cai, Y. Nakayama, T. Shiono, Macromolecules 2006, 39,
031–2033.
1
8 T. Shiono, M. Sugimoto, T. Hasan, Z. Cai, T. Ikeda, Macro-
molecules 2008, 41, 8292–8294.
2
6
full-matrix least-squares methods on F using SHELXS-97
1
9 T. Tada, Z. Cai, Y. Nakayama, T. Shiono, Macromol. Chem.
program package. The positions of all non-hydrogen atoms
were found from a difference Fourier electron density map
and refined anisotropically. All hydrogen atoms were placed
in calculated positions (CAH ¼ 0.95 Å) and constrained to
ride on their respective carbon atoms. Although the pres-
Phys. 2010, 211, 2132–2137.
20 Z. Cai, R. Harada, Y. Nakayama, T. Shiono, Macromolecules
2010, 43, 4527–4531.
21 H. Hagimoto, T. Shiono, Ikeda, T. Macromol. Rapid Com-
mun. 2002, 23, 73–76.
ence of Et O as a crystalline solvent was indicated from
22 K. Soga, T. Uozumi, T. Arai, S. Nakamura, Macromol. Rapid
Commun. 1995, 16, 379–385.
2
1
the H NMR data, Et O could not properly be located, pos-
2
2
3 D. R. Neithamer, J. C. Stevens, (Dow Chemical Co.). U.S.
Patent 5, 399, 635, March 21, 1995.
4 J. Okuda, F. J. Schattenmann, S. Wocadlo, W. Massa, Orga-
nometallics 1995, 14, 789–795.
5 K. Patsidis, H. G. Alt, W. Milius, S. J. Palackal, J. Organo-
met. Chem. 1996, 509, 63–71.
sibly due to partial elimination from the crystal and/or
disorder.
2
Crystal and refinement data for 6: C H NSiTi, formula weight
3
7 59
¼
593.87, tetragonal, a ¼ 35.8207(17) Å, c ¼ 12.1603(6) Å, V ¼
2
3
1
5603.2(12) Å , space group I4 /a (#88), Z ¼ 16, d ¼ 1.011
1
calc
3
g/cm , R (R ) ¼ 0.099 (0.142) for 11388 diffraction data [I >
€
€
w
26 G. M. Sheldrick, SHELXS-97, Universitat Gottingen:
5r(I))] and 421 variables, and GOF ¼ 1.001.
Germany, 1997.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1223–1229
1229