Synthesis and characterization of tridentate [O-N(H)X] titanium complexes and their applications in olefin polymerization

Article abstract of DOI:10.1002/pola.26643

A series of [O^-N(H)X]TiCl₃ complexes derived from (arylamino)methylene phenol are prepared. The molecular structures of the complexes are characterized by ¹H NMR, ¹³C NMR, and X-ray analysis. Upon activation with modified methylaluminoxane (MMAO), the titanium complexes display high thermal stability and single-site like ethylene (co)polymerization behavior at the temperatures of up to 150 °C. 1-Octene and 1-octadencene prove suitable to be incorporated into polyethylene backbone at 110 °C and the highest activity of 1.89 × 10⁶ g/mol(Ti)·h·atm can be achieved. The pendant group X has great influence on the catalytic behaviors of the complexes, and PPh₂ proves to be the optimal group.

Full text of DOI:10.1002/pola.26643

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
Synthesis and Characterization of Tridentate [O2N(H)X] Titanium
Complexes and Their Applications in Olefin Polymerization
Da-Wei Wan,1 Zhou Chen,2 Yan-Shan Gao,2 Qi Shen,1 Xiu-Li Sun,2 Yong Tang2
1School of Chemistry and Chemical Engineering, Soochow University, Suzhou, 215123 China
2State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
345 Lingling Lu, Shanghai 200032, China
Correspondence to: X.-L. Sun (E-mail: xlsun@sioc.ac.cn)
Received 15 November 2012; accepted 9 February 2013; published online 13 March 2013
DOI: 10.1002/pola.26643
ABSTRACT: A series of [O2N(H)X]TiCl3 complexes derived from
(arylamino)methylene phenol are prepared. The molecular struc-
tures of the complexes are characterized by 1H NMR, 13C NMR,
and X-ray analysis. Upon activation with modified methylalumi-
noxane (MMAO), the titanium complexes display high thermal
stability and single-site like ethylene (co)polymerization behav-
ior at the temperatures of up to 150 ꢀC. 1-Octene and 1-octaden-
cene prove suitable to be incorporated into polyethylene
backbone at 110 ꢀC and the highest activity of 1.89 3 106 g/mol
(Ti)ꢁhꢁatm can be achieved. The pendant group X has great
influence on the catalytic behaviors of the complexes, and PPh2
C
V
proves to be the optimal group. 2013 Wiley Periodicals, Inc.
J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2495–2503
KEYWORDS: catalyst; copolymerization; high temperature; poly-
olefins; titanium complexes
incorporation ratio of 1-octene with an activity of 7.4 3 105
g/mol(Ti)ꢁhꢁatm could be achieved at 110 ꢀC when 4a/
MMAO was used. In this article, we wish to report the results
in details.
INTRODUCTION Thermal stability of catalysts for olefin is
extremely important for their application in industry.1 So far,
several metallocene catalysts such as CGC-type complexes
and Ph2C(Cp)(Flu)ZrCl2/(Me2PhNHꢁ(B(C6F5)4)-(iBu3Al) were
disclosed to be able to produce polyolefins in high activities
at temperatures above 100 ꢀC.2 Although non-metallocene
complexes3–11 such as Ni(II)- and Pd(II)-based diimine com-
plexes,4 salicylaldiminato complexes,5 Fe(II) and Co(II) based
pyridine diimine complexes,6 phenoxy titanium half-sandwich
complexes,7 amine bis(phenolate) metals complexes,8 and
bis(b-enaminoketonato)metal complexes9 prove superior in
catalyzing the olefins polymerizations, only a few catalysts
was highly thermally stable and active when the polymeriza-
tion was run at temperatures higher than 100 C. We have
developed a serial of [O2NX]TiCl3 (X 5O, S, P, Se) complexes
based on either salicylaldiminato or b-carbonylenamine,
which are highly active for the ethylene polymerization and
copolymerization at 80 and 100 ꢀC respectively in the pres-
ence of MMAO.12 In view of unstability of the imine ligand
skeleton under the polymerizaion conditions, very recently,13
we further designed and synthesized [O2N(H)X]TiCl3 (X 5 S,
P) titanium complexes. In the presence of MMAO,
[O2N(H)X]TiCl3 complexes show good thermal stability and
are highly active in catalyzing the ethylene polymerization
even at 150 ꢀC. Both 1-octene and 1-octadecene could be
copolymerized with ethylene smoothly. 5.9 mol%
EXPERIMENTAL
General Informations
All air and moisture sensitive operations were carried out
under nitrogen atmosphere using Schlenk techniques. 1H NMR,
13C NMR, and 31P NMR spectra were recorded on Varian Mer-
cury 300 Spectrometer or Varian 400 MR spectrometer. Mass
spectra were carried out with a HP5989A spectrometer. Ele-
mental analyses were performed by the Analytical Laboratory
of Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences. Number-average molecular weight (Mn), weight aver-
age molecular weight (Mw), and molecular weight dispersity
10
ꢀ
ꢀ
(Mw/Mn) values of polymers were determined at 150 C by a
Polymer Laboratories-Gel Permeation Chromatograph (PL-GPC
220) using 1,2,4-trichlorobenzene as the mobile phase with a
flow rate of 1.0 mL/min. Polystyrene standards were used for
calibrations. LS type columns of PLgel 10 mm MIXED-B and
MIXED-D were used in series. Polymerization was carried out
in stainless-steel autoclave (Parr Instrument Company, 452HC).
1H NMR and 13C NMR data of polymer recorded on Varian 400
ꢀ
MR spectrometer at 110 C using o-dichlorobenzene-d4 as the
Additional Supporting Information may be found in the online version of this article.
C
V
2013 Wiley Periodicals, Inc.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503
2495

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
solvent. The melting temperature (Tm) was measured by
added lithium aluminum hydride (0.09 g, 2.27 mmol). After
refluxing for 2 h, the reaction mixture was quenched by
water, washed with 20% aqueous NaOH. The organic layer
was separated and concentrated. The product was afforded
by concentration of solution. Yield: 1.04 g (76 %)
differential scanning calorimetry DSC (Q200, TA) at a heating
21
ꢀ
ꢀ
rate of 10 C min from 280 to 200 C. X-ray were collected
at 293 K on a Bruker SMART 1000 CCD diffractometer using
Mo K (k 5 0.71073 Å) radiation. An empirical absorption was
applied using the SADABS program. All molecular structures
were solved by direct methods and subsequent Fourier differ-
ence techniques and refined anisotropically for all nonhydrogen
atoms by full-matrix least-squares calculations on F2 using the
SHELXTL program package. All hydrogen atoms were geometri-
cally fixed using the riding Model. Toluene, hexane, dichlorome-
thane (CH2Cl2) and other solvents were purified by MB SPS-
1H NMR (300 MHz, CDCl3, d): d 7.66–7.60 (m, 2H), 7.54–
7.38 (m, 8H), 7.26–6.95 (m, 8H), 6.90–6.54 (m, 4H), 5.05
(brs, 1H, NH), 4.33 (d, J 5 5.4 Hz, 2H, -CH2). 31P NMR (121
MHz, CDCl3, d): d 220.1. 13C NMR (75 MHz, CDCl3, d): d
152.5, 150.2, 150.0, 139.4, 137.6, 134.9, 134.8, 134.0, 133.8,
133.5, 132.3, 132.0, 131.9, 131.8, 130.9, 130.5, 129.6, 129.2,
128.9, 128.8, 128.6 (5), 128.6 (0), 128.3, 127.9, 127.1, 124.9,
124.1, 122.2, 122.1, 119.9, 119.5, 112.8, 46.9 IR (KBr, cm21):
m 5 3674 (w), 2988 (s), 2901 (s), 2536 (s), 1585 (m), 1431
(m), 1529 (m), 1067 (m), 741 (s), 693 (s). MS (ESI, m/z):
460 [M1H]1. HRMS (ESI, m/z): [M1H]1 calcd for
ꢀ
800 system (column MB-KOL MT2–150 C). Trimethylbenzene
was purchased from Sinopharm and distilled with sodium
before use. Norbornene (NBE) was purchased from Alfa Aesar
and distilled over sodium before use. MMAO (MMAO-3A, hep-
tane solution) was purchased from Akozo Nobel. Ethylene
(>99.95%) was further purified (O2 < 1 ppm, H2O < 1 ppm)
before use by PEN molecular sieves from Dalian Samat Chemi-
cals. The comonomers were purchased from Alfa Aesar
(purity > 98%), distilled with sodium before use. 3a was syn-
thesized according to literature.12(a) The supplementary mate-
rial available via the Internet at http://www.interscience.
wiley.com/jpages/0887 -624X/suppmat.
C
31H27NOP11: 460.1814 (M1H)1, found: 460.1825.
Synthesis of 2,4-Di-tert-butyl-6-(1-(2-(diphenylphosphino)
phenylamino)22,2-dimethylpropyl)phenol (3f)
To a solution of 1-[3,5-bis(1,1-dimethylethyl)22-hydroxy-
phenyl]-2,2-dimethyl-1-propanone (1.0 g, 3.44 mmol),
2-(diphenylphosphino)aniline (1.15 g, 4.13 mmol) and Et3N
(5 mL) in dichloromethane (5 mL) was added TiCl4 (0.41 g,
ꢀ
ꢀ
2.0 mmol) at 0 C. After stirring for 2 h at 0 C, the reaction
mixture was quenched with water. The resulting solid was
collected and washed with dichloromethane. After purifica-
tion by flash column chromatography (base Al2O3, petroether
as eluant), the obtained yellow solid was reduced by lithium
aluminum hydride (0.03 g, 0.89 mmol) in THF under reflux-
ing for 2 h. The reaction mixture was quenched by water,
washed with 20% aqueous NaOH. The organic layer was
separated and concentrated. The pure product was precipi-
tated by concentration of solution. Yield: 0.36 g (73 %).
Synthesis of 2,4-Bis(t-butyl)26-(2-(diphenylphosphinyl)
phenyl)aminomethyl phenol (3b)
To a solution of 2,4-bis(tert-butyl)26-(2-(diphenylphosphi-
no)phenyl)aminomethyl phenol (0.36 g, 0.73 mmol) in tetra-
hydrofuran (THF) was added hydrogen peroxide (0.03 g,
0.88 mmol) at 0 ꢀC. After 0.5 h, the reaction mixture was
extracted with diethyl ether. The organic layer was washed
with water and dried over sodium sulfate. White solids
were obtained by concentration of the solution. Yield: 0.37 g
(100 %).
1H NMR (300 MHz, CDCl3, d): d 8.93 (s, 1H, -OH), 7.40–7.31
(m, 10H), 7.16–7.06 (m, 2H), 6.91–6.86 (m, 1H), 6.76–
6.66(m, 3H), 5.41 (d, J 5 8.4 Hz, 1H, ANH), 3.91 (s, 1H,
ACH2), 1.31 (s, 9H, AC(CH3)3), 1.28 (s, 9H, AC(CH3)3), 0.92
(s, 9H, AC(CH3)3). 31P NMR (121 MHz, CDCl3, d): d 220.8.
13C NMR (75.5 MHz, d): d 154.0, 150.1, 149.8, 139.5, 135.9,
135.0, 134.9, 134.3, 134.2, 134.1, 134.0, 133.9, 133.7, 130.5,
129.2(5), 129.2(0), 128.9, 128.8, 128.7, 125.5, 123.5, 123.4,
122.2, 121.6, 120.2, 114.1, 72.0, 36.9, 34.8, 34.0, 31.7, 29.5,
27.4. IR (KBr, cm21): m 5 3358 (w), 2958 (s), 2926 (s), 2873
(s), 1720 (s), 1587 (m), 1469 (m), 1223 (m), 1049 (s), 880
(s), 742 (m), 692 (s). (MS (ESI, m/z): 552 [M1H]1. HRMS
1H NMR (300 MHz, CDCl3, d): d 7.66–7.57 (m, 5H), 7.50–
7.36 (m, 4H), 7.18 (s, 1H), 7.11 (s, 1H), 6.98–6.95 (s, 1H),
6.88–6.76 (m, 3H), 5.30 (brs, 1H, NH), 4.31 (d, J 5 4.5 Hz,
2H, CH2), 1.28 (s, 9H, C(CH3)3), 1.26 (s, 9H, C(CH3)3). 31P
NMR (121 MHz, CDCl3, d): d 36.5. 13C NMR (75 MHz, CDCl3,
d): d 152.9, 152.2(2), 152.2(0), 141.4, 136.2, 133.7(4),
133,7(2), 133.3, 133.2, 132.2(1), 132.2(0), 132.0, 131.9,
130.6, 128.8, 128.6, 123.8, 123.3, 122.2, 118.4, 118.3, 117.2,
115.8, 114.0, 113.9, 47.9, 34.7, 34.1, 31.6, 29.6. IR (KBr,
cm21): m 5 3541 (w), 3052 (s), 2919 (s), 2851 (s), 1586 (m),
1496 (m), 1431 (s), 1260 (m), 1161 (s), 1088 (m), 1026 (s),
741 (s), 694 (s). MS (ESI, m/z): 512 [M1H]1. HRMS (ESI,
m/z): [M1H]1: calcd for C33H39NO2P11: 512.2719 [M1H]1;
found: 521.2713.
(ESI, m/z): [M1H]1 calcd for C37H47NOP11
[M1H]1, found: 552.3390.
: 552.3375
Synthesis of Complex 4 (4c as an Example)
To a solution of 3c (0.40 g, 1 mmol) in toluene (5 mL) was
added TiCl4 (0.21 g, 1.1 mmol) in toluene (5 mL) at room
temperature. The resulting mixture was sꢀtirred for 24 h at
room temperature and then heated to 50 C for further 2 h.
After filtration, the solvent was removed under reduced
pressure to afford red powder, which was recrystallized in
toluene/hexane (v/v: 10/1) to give complex 4c.
Synthesis of 2-Phenyl-6-(2-
(diphenylphosphino)phenylaminomethyl)-phenol (3e)
To a solution of 2-hydroxy-(1,10-biphenyl)23-carbaldehyde
(0.59 g, 3.0 mmol) and 2-(diphenylphosphino)aniline (0.83 g,
3.0 mmol) in ethanol was added a drop of acetic acid, the
resulting mixture was refluxed for 8 h. The solid was
collected and dissolved in THF. To the resulting solution was
2496
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
4b 0.29 g (88 % yield). 1H NMR (300 MHz, CDCl3, d): d
8.09–8.02 (m, 2H), 7.93–7.86 (m, 2H), 7.76–7.68 (m, 4H),
7.56–7.51 (m, 4H), 7.37 (s, 1H), 7.19–7.04 (m, 3H), 5.50
(brs, 1H), 5.12 (brs, 1H), 4.14 (d, J 5 14.7 Hz, 1H), 1.61 (s,
9H, -C(CH3)3), 1.35 (s, 9H, -C(CH3)3). 31P NMR (121 MHz,
CDCl3): d 40.8. 13C NMR (75 MHz, CDCl3, d): d 162.8, 152.9,
146.9, 134.7, 134.6, 134.4, 133.6, 133.5, 133.5, 133.4, 133.2,
129.7, 129.5, 129.3, 128.2, 127.3, 127.1, 125.8, 125.5, 124.3,
123.9, 119.8, 118.9, 118.4, 117.5, 50.8, 35.5, 34.8, 31.6, 30.5.
IR (KBr, cm21): m 5 3259 (s), 3055 (m), 2955 (s), 2864 (s),
1596 (m), 1451 (m), 1236 (s), 1172 (m), 1060 (m), 913 (s),
751 (s). Anal. Calcd for C33H37Cl3NO2PTi: C, 59.62; H, 5.61;
N, 2.11; found: C, 59.90; H, 5.24; N, 1.78.
(75 MHz, CDCl3, d): d 159.5, 157.6, 157.3, 144.9, 135.6,
135.5, 135.0, 133.6, 133.0, 132.9, 130.9, 130.8, 130.5, 130.3,
129.9, 129.4, 129.0, 128.6, 128.5, 128.3, 128.2, 128.0, 126.6,
125.3, 123.4, 82.3, 37.5, 35.0, 34.3, 31.5, 30.5, 28.6. IR (KBr,
cm21): m 5 3254 (s), 3057 (s), 2959 (s), 2906 (s), 2868 (s),
1589 (m), 1480 (s), 1436 (s), 1363 (m), 1261 (m), 1089
(m), 1027 (m), 968 (m), 871 (m), 768 (m). Anal. calcd for
C37H45Cl3NOPTi: C, 63.04; H, 6.43; N, 1.99; Found: C, 63.78;
H 6.78; N, 1.75.
General Procedure for Ethylene Polymerization
A 300 mL dried stainless-steel autoclave was charged with sol-
vent (50 mL) and stirred for 30 min (IKA RCT stirrer, stirring
rate of 500 rpm) at the desired temperature. Desired amount
of MMAO (1.88 M in heptane) was added and the solution was
stirred for 5 min. Then, catalyst (5 mmol, 1 mmol mL21 in tolu-
ene) was added and followed by the feeding of ethylene to the
desired pressure. By the time to end the polymerization, the
autoclave was vented and the reaction mixture was poured
into acidified ethanol (200 mL, 10% HCl) and stirred for 12 h.
The polymer was filtered, collected, washed with ethanol, and
dried to constant weight under vacuum at 70 ꢀC.
4c 0.51 g (89 % yield). 1H NMR (300 MHz, CDCl3, d): d
7.66–7.61 (m, 3H), 7.54 (t, J 5 7.5 Hz, 2H), 7.46–7.44 (m,
1H), 7.36–7.35 (m, 2H), 7.19–7.17 (m, 2H), 6.68 (dd, J 5 3.9
Hz, 5.7 Hz, 1H), 5.68 (brs, 1H), 4.94–4.72 (m, 2H), 1.55 (s,
9H, -C(CH3)3), 1.33 (s, 9H, -C(CH3)3). 13C NMR (75 MHz,
CDCl3, d): d 161.6, 154.9, 154.4, 148.0, 137.8, 135.9, 130.7,
130.3, 129.4, 129.0, 128.5, 128.2, 125.3, 124.8(2), 124.8(0),
124.3, 123.7, 115.4, 54.6, 35.5, 34.8, 31.4, 30.2. IR (KBr,
cm21): m 5 3158 (m), 2960 (s), 2868 (s), 1589 (s), 1489 (s),
1236 (m), 1172 (m), 861 (s), 754 (m), 691 (s). Anal. Calcd
for C27H32Cl3NO2Ti: C, 58.24; H, 5.79; N, 2.52; found: C,
58.68; H, 6.07; N, 2.11.
General Procedure for Ethylene Copolymerization
A 300 mL dry stainless-steel autoclave was charged with
solvent and kept at the desired temperature for 30 min. The
comonomer and desired amount of MMAO (1.88 M in
heptane) was added and the solution was stirred for 5 min.
Adding catalyst (5 mmol, 1 mmol mL21 in toluene) to the
reaction system and the autoclave was fed with ethylene to
the desired pressure. The polymerization was quenched by
acidified ethanol (200 mL, 10% HCl). The polymer was
filtered, collected, washed with ethanol and dried to constant
1
4d 1.04 g (92% yield). H NMR (300 MHz, CDCl3, d): d 7.75–
7.72 (m, 1H), 7.56 (t, J 5 7.5 Hz, 1H), 7.42–7.29 (m, 3H),
7.24–7.16 (m, 4H), 7.11–7.09 (m, 1H), 6.82 (s, 1H), 6.30–
6.65 (brs, 1H), 5.10 (brs, 1H), 4.32 (brs 1H), 1.40 (s, 9H, -
C(CH3)3), 1.22 (s, 9H, AC(CH3)3). 13C NMR (75 MHz, CDCl3,
d): d 160.2, 147.2, 137.8, 136.1, 133.3, 131.4, 130.1, 130.0,
129.4, 129.3, 129.0, 128.9, 128.5, 128.2, 127.1, 125.3, 125.0,
124.3, 58.0, 35.1, 34.6, 31.3, 29.8. IR (KBr, cm21): m 5 3122
(w), 2957 (m), 2868 (s), 1582 (m), 1479 (s), 1441 (s), 1238
(s), 1127 (m), 887 (s), 750 (m). Anal. Calcd for
ꢀ
weight under vacuum at 70 C.
RESULTS AND DISCUSSION
C
27H32Cl3NO2Tiꢁ1.5C6H5CH3: C, 63.08; H, 6.63; N, 1.96;
Synthesis and Characterization of Ligands and Titanium
Complexes
found: C, 62.53; H, 6.36; N, 1.72.
4e 0.55 g (90 % yield). 1H NMR (300 MHz, CDCl3, d): d
7.79–7.32 (m, 13H), 7.19–7.18 (m, 3H), 6.84–6.81 (m, 6H),
6.46 (brs, 1H), 5.55–5.46 (m, 1H), 4.41–4.32 (m, 1H). 31P
NMR (121 MHz, CDCl3): d 17.6. 13C NMR (75 MHz, CDCl3, d):
d 159.2, 151.7, 149.1, 138.0, 137.8, 136.6, 136.3, 135.6,
134.4, 134.3, 133.7, 132.2, 132.1. 131.8, 131.0, 130.6, 130.1,
130.0, 129.9, 129.6, 129.4, 129.0, 128.7, 128.6, 128.5, 128.4,
128.2, 127.9, 127.6, 127.5, 127.1, 126.8, 126.6, 126.4, 125.3,
123.5, 57.8. IR (KBr, cm21): m 5 3352 (w), 3159 (s), 3056
(s), 1586 (m), 1481 (m), 1436 (m), 1229 (m), 1122(m), 911
(s), 785 (s), 639 (s). Anal. Calcd for C31H25Cl3NOPTi: C,
60.77; H, 4.11; N, 2.29; found: C, 59.95; H, 4.11; N, 2.55.
(Arylamino)methylene phenol was synthesized from the cor-
responding salicylaldehydes and aniline. As shown in Scheme
1, the condensation reaction between salicylaldehyde and
substituted aniline in the presence of either catalytic amount
of acid or TiCl4 generated imine compounds smoothly. With-
out separation and further purification, the in situ formed
imine compounds could be reduced into ligands 3 readily in
73% to quantitative yields. 3b was obtained quantitatively
by oxidation of 3a. Without the pretreatment 3 with base,
the reaction between 3 and excess of TiCl4 in toluene
at room temperature gave complexes 4 as red solids in
81–93% yields. All compounds were well characterized by
1H NMR, 13C NMR and elemental analysis. 1H NMR of the
complexes 4 show that the chemical shift of CH2-N move
toward downfield relative to the corresponding ligands,
indicating the coordination effect of nitrogen to the metal.
The 13C NMR signal of C-N in 4f at 80 ppm, relative to those
in complex 4b-e (around 50 ppm), suggesting an apparent
fragment distortion induced by steric R3 group. For
4f 0.57 g (81% yield). 1H NMR (300 MHz, CDCl3, d): d 7.85
(t, J 5 8.7 Hz, 2H), 7.70–7.31 (m, 7H), 7.19–7.12 (m, 1H),
6.98 (t, J 5 6.9 Hz, 2H), 6.86–6.80 (m, 1H), 6.45(4)26.45(0)
(m, 1H), 5.97–5.96 (m, 1H), 4.08 (s, 1H), 1.32 (s, 9H,
AC(CH3)3), 1.19 (s, 9H, AC(CH3)3), 1.13 (s, 9H,
AC(CH3)3).31P NMR (121 MHz, CDCl3, d): d 12.8. 13C NMR
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503
2497

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
FIGURE 2 The molecular structure of 4b. Selected bond
˚
lengths (A) and angles(deg) Ti(1)AO(1), 1.772(5); Ti(1)AN(1),
2.326(6); Ti(1)AO(2), 1.993(3); Ti(1)ACl(1), 2.326(3); Ti(1)ACl(2),
2.249(2); Ti(1)ACl(3), 2.362(3); O(1)AC(1), 1.359(8); C(6)AC(7),
1.497(10);
C(7)AN(1),
1.491(9);
N(1)AC(8),
1.442(9);
94.19(18);
90.09(18);
O(1)ATi(1)AN(1),
N(1)ATi(1)ACl(3),
83.5(2);
O(1)ATi(1)ACl(3),
O(1)ATi(1)ACl(1),
81.35(18);
N(1)ATi(1)ACl(1), 89.28(17); Cl(3)ATi(1)ACl(1), 169.17(10);
O(1)ATi(1)AO(2), 161.8(2); N(1)ATi(1)AO(2), 78.6(2).
SCHEME 1 Synthesis of ligands and complexes.
for example, the geometry around the titanium of 4c adopts
a distorted octahedron geometry and O(1)AO(2)ACl(2)A
Cl(3) are nearly coplanar. Titanium deviates from the plane
0.2380 (0.0012) Å. Three chlorine atoms are in a mer
position: Cl(3)ATi(1)ACl(1) angle is 102.56(5)ꢀ, Cl(2)ATi(1)
ACl(1) and Cl(2)ATi(1)ACl(3) are 95.00(5)ꢀ and 91.30(5)ꢀ,
indicating that three chlorines are located in a cis position to
each other, which is beneficial to the insertion of olefins. The
complexes 4e and 4f, 31P NMR signals shift downfield from
around 220 ppm to 17.6 and 12.8 ppm separately, demon-
strating that phosphorus is probably coordinated to the
metal. The 31P NMR signals of 3b and 4b appeared at 36.5
and 40.8 ppm, respectively.
Molecular structures of 4 (Figs. 1–4) were further deter-
mined by X-ray diffraction (Table 1). As shown in Figure 1
FIGURE 3 The molecular structure of 4d. Selected bond
FIGURE 1 The molecular structure of 4c. Selected bond lengths
˚
˚
lengths (A) and angles(deg) Ti(1)AO(1), 1.791(2); Ti(1)AN(1),
(A) and angles(deg). Ti(1)-O(1), 1.809(3); Ti(1)AN(1), 2.225(3);
2.249(3);
Ti(1)AS(1),
2.6215(3);
Ti(1)ACl(1),
2.2599(12);
Ti(1)AO(2), 2.304(3); Ti(1)ACl(1), 2.2612(13); Ti(1)ACl(2),
2.3813(13); Ti(1)ACl(3), 2.2610(12); O(1)AC(1), 1.373(4);
C(6)AC(7), 1.491(6); C(7)AN(1), 1.520(4); N(1)AC(8), 1.469(5);
Ti(1)ACl(2), 2.2439(13); Ti(1)ACl(3), 2.3569(11); O(1)AC(1),
1.365(4); C(6)AC(7), 1.508(5); C(7)AN(1), 1.499(5); N(1)AC(8),
1.461(5);
162.61(9); N(1)ATi(1)ACl(3), 80.94(8); O(1)ATi(1)ACl(1), 96.41(9);
N(1)ATi(1)ACl(1), 93.04(9); Cl(3)ATi(1)ACl(1), 92.14(4);
O(1)ATi(1)AS(1), 80.03(8); N(1)ATi(1)AO(2), 74.94(8).
O(1)ATi(1)AN(1),
83.51(11);
O(1)ATi(1)ACl(3),
O(1)ATi(1)AN(1),
N(1)ATi(1)ACl(3),
N(1)ATi(1)ACl(1),
83.31(12);
96.60(9);
O(1)ATi(1)ACl(3),
O(1)ATi(1)ACl(1),
Cl(3)ATi(1)ACl(1),
96.90(9);
97.89(10);
102.56(5);
163.19(9);
O(1)ATi(1)AO(2), 86.57(11); N(1)ATi(1)AO(2), 74.67(11).
2498
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
TABLE 2 Crystal Data Comparisons of 4b, 4c, 4d, and 4f
Bond angle (ꢀ)
4b
4c
4d
4f
C7AN1AC8
O1ATiAX
116.9(6)
161.8(2)
113.2(3)
113.3(3)
80.03(8)
110.0(4)
86.57(11)
90.89(13)
4b, 4d, and 4f showed similar molecular structures to that
of 4c. The geometry around titanium is distorted octahedron
and three chlorines locate in a mer position. The sums of
angles around N1 are smaller than 350ꢀ, indicating that N1
adopts a sp3 hybridization. When a tBu group was intro-
duced on C7 (4f), N(1), P(1), Cl(2), and Cl(3) are coplanar
and the centre titanium deviates from the plane 0.1154
(0.0016) Å. The bond angle of C7AN1AC8 is 110(4)ꢀ, while
that of complex 4a is 117ꢀ.12(a) In the case of PPh2@O was
introduced as a pendant group, the oxygen coordinated with
titanium to form two six-membered rings. The bond length
of Ti-O(2) is shorter than that in 4c (1.993(3) versus
2.304(3) Å). Regardless of the different substitution on the
fragment of the ligand, similar bond angle of C7AN1AC8
was observed for the four molecules. However, bond angle of
O1ATiAX (X 5O, S, P) differs considerably from each other
(Table 2).
FIGURE 4 The molecular structure of 4f. Selected bond
˚
lengths (A) and angles(deg) Ti(1)AO(1), 1.777(4); Ti(1)AN(1),
2.295(5); Ti(1)AP(1), 2.624(2); Ti(1)ACl(1), 2.355(2); Ti(1)ACl(2),
2.2581(19); Ti(1)ACl(3), 2.3569(11); O(1)AC(1),1.374(6); C(6)AC(7),
1.518(7); C(7)AN(1), 1.525(6); N(1)AC(8), 1.460(7); O(1)ATi(1)A
N(1), 80.80(16); O(1)ATi(1)ACl(3), 97.57(13); N(1)ATi(1)ACl(3),
101.66(13); O(1)ATi(1)ACl(1), 158.24(14); N(1)ATi(1)ACl(1),
77.50(12); Cl(3)ATi(1)ACl(1), 88.32(7);O(1)ATi(1)AP(1), 90.89(13);
N(1)ATi(1)AP(1), 74.79(12).
sum of angles around N1 (C7AN1ATi1, C8AN1ATi1, and
C7AN1AC8) is 339.9ꢀ, which means that the nitrogen is sp3
hybridization. The bond length of Ti(1) AN(1) is longer than
that of the corresponding phenoxyl-imine complex (2.225(3)
Å vs. 2.152(4) Å).12(c) The bond length of Ti1AO2 (2.304(3) Å)
is slightly longer than the sum of the covalent radii of titanium
and oxygen (rcov(Ti) 5 1.60 Å, rcov(O) 5 0.66 Å),14 suggesting a
weak interaction existed between titanium and pendant ether
group.
Ethylene Polymerization
Upon activation by MMAO, 4a–f were evaluated at high tem-
ꢀ
perature (110–150 C) for ethylene polymerization (Table 3).
High activity and high molecular weight were observed
when the polymerization was preceded under 1 atm ethyl-
ene pressure. The catalysts structure, Al/Ti ratio, reaction
temperature, and ethylene pressure influenced both the
activities and the molecular weight of the resulting
TABLE 1 Crystal Data and Details of Data Collection for 4b, 4c, 4d, and 4f
4b
4c
4d
4f
Formula
C
33H37Cl3NO2PTi
C34H40Cl3NO2Ti
648.92
C37.5H43.5Cl3NOSTi
710.54
C40.5H48Cl3NOPTi
750.02
Fw (g/mol)
Crystsyst
664.86
Monoclinic
P2(1)/c
11.360(3)
13.042(4)
21.950(6)
3252.1(15)
4
Triclinic
P-1
Triclinic
P-1
Monoclinic
C2/c
Space group
˚
a, A
10.365(3)
14.244(3)
14.322(6)
1791.2(3)
2
10.4147(10)
14.2401(14)
14.3818(14)
1827.3(11)
2
41.287(16)
10.704(4)
18.274(7)
7836(5)
˚
b, A
˚
c, A
3
˚
V, A
Z
8
Dcalcd, Mg/m3
2h range, deg
F(1000)
1.358
1.203
1.291
1.271
1.82 to 25.50
1384
1.61 to 25.05
680
1.66 to 26.00
745
1.97 to 25.05
3152
Reflections
15465/6030
11082/6219
10031/7052
24963/6935
collected/unique
[R(int) 5 0.1286]
[R(int) 5 0.0506]
[R(int) 5 0.0239]
[R(int) 5 0.1209]
Data/restraints/parameters
Goodness of fit
R1 (I > 2r(I))
6030/0/381
0.939
6219/0/370
0.977
7052/4/398
1.027
6935/84/481
1.027
0.0792
0.0797
0.0588
0.0757
wR2 (I > 2r(I))
0.2798
0.2142
0.1732
0.2279
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503
2499

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
TABLE 3 Polymerization of ethylene under high temperaturea
Tp
(ꢀC)
Time
(min)
Yield
(g)
Entry
Cat.
Al/Ti
Solvent
Activityb
Mw
Mw/Mn
c,d
c
1
4a
4a
4a
4a
4a
4a
4a
4a
4b
4c
4d
4e
4f
200
500
1000
2000
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
110
110
110
110
110
130
150
150
110
110
110
110
110
30
2
2
Toluene
0.22
0.90
0.77
0.62
0.73
0.56
–
1.32
5.40
4.61
3.73
4.39
3.37
–
9.3
2.3
2.8
2.4
2.3
2.7
2.2
–
2
Toluene
12.6
10.4
3.6
3
2
Toluene
4
2
Toluene
5
2
Trimethylbenzene
Trimethylbenzene
Trimethylbenzene
Trimethylbenzene
Toluene
2.5
6
2
1.7
7
8e
2
–
2
0.45
0.22
–
0.54
1.32
–
15.9
10.4
–
2.3
2.4
–
9
2
10e
11e
12
13
14
15
16
17
18
19
20
2
Toluene
2
Toluene
0.19
0.16
0.72
0.18
0.45
0.81
1.13
2.05
2.86
3.16
0.22
0.96
4.32
1.08
2.70
4.86
6.78
4.92
2.29
1.26
18.5
9.8
3.8
2.3
2.0
1.8
1.8
1.9
2.6
2.9
2.9
3.1
2
Toluene
2
Toluene
3.8
4a
4a
4a
4a
4a
4a
4a
2
Toluene
24.3
19.3
18.0
15.8
13.7
15.1
18.2
50
2
Toluene
70
2
Toluene
90
2
Toluene
110
110
110
5
Toluene
15
30
Toluene
Toluene
a
d
Solvent, 50 mL; cat., 5 lmol; 1 atm ethylene.
106 g/molꢁhꢁatm.
104 g/mol.
5 atm ethylene.
b
c
e
Determined by GPC.
polyethylene. When the ethylene polymerization was cata-
lyzed by 4a at 110 C and 200 Al/Ti ratio, an activity of 1.32
titanium is a more important factor than electronic property
to influence the catalytic behavior of the complexes. When
ꢀ
3 106 g/mol(Ti)ꢁhꢁatm was obtained. Increasing the molar ra-
tio of Al/Ti to 500 resulted in the activity increasing (5.40 3
106 g/mol(Ti)ꢁhꢁatm, entry 1 vs. 2). However, no apparent ele-
vation could be observed when the ratio was further improved
(entries 2–4). Trimethylbezene was also a suitable solvent
two Bu groups at R1 and R2 positions were replaced by H
t
and phenyl groups separately (4b), a reduced activity of
0.96 3 106 g/mol(Ti)ꢁhꢁatm was produced (entry 12). Intro-
ducing a tert-butyl group on (Ar)-C7-N1 fragment (4f)
results in the structure of complex deviates greatly in com-
parison with that of 4a,10(a) however, it catalyzed ethylene
polymerization quite smoothly to give PE in an activity of
ꢀ
(entry 5). The polymerization carried out at 130 C in trime-
thylbenzene under 1 atm ethylene pressure generated PE in a
high activity of 3.37 3 106 g/mol(Ti)ꢁhꢁatm. Though no poly-
mer could be separated when the polymerization was pro-
6
ꢀ
4.32 3 10 g/mol(Ti)ꢁhꢁatm at 110 C and 500 Al/Ti ratio.
ꢀ
The thermal stability of the catalysts could be established
by comparing the polymerization results under different
temperatures. As shown in Table 3, the activity of 4a/
MMAO was dependent on the polymerization temperature.
For example, the temperature rise led to enhancement first
and then decrease of activity. The highest activity of 6.78 3
106 g/mol(Ti)ꢁhꢁatm was at 90 ꢀC (entries 14–18 vs. 2).
Further increasing the temperature to 110 ꢀC reduced the
activity slightly (entry 2 vs. 18). When the polymerization
time was prolonged to 5 min., a high activity of 4.9 3 106
g/mol(Ti)ꢁhꢁatm could be achieved. Though the polymeriza-
tion mixture became more and more viscous, satisfied activ-
ities were still achieved even if the polymerization was
carried out for 30 min. at 110 ꢀC (entries 18–20 vs. 2).
These results suggested that the catalytic species is quite
ceeded under 1 atm ethylene pressure at 150 C (entry 7), an
activity of 0.54 3 106 g/mol(Ti)ꢁhꢁatm was achieved at 150 ꢀC
under 5 atm pressure (entry 8).
The structures of the complexes have great impact on the ac-
ꢀ
tivity. 4c was totally inactive to the polymerization at 110 C
even under 5 atm pressures. Replacing the pendant group
from OPh group with SPh (4d) generated a moderate activity
(entry 11). As X-ray analysis revealed that O2 atom in 4c is
sp2 hybridization and the S atom in 4d is sp3 hybridization,
a synergistic effect between the steric hindrance and elec-
tronic properties of the metal center was probably the rea-
son for different behavior of polymerization. 4b, in which
O@PPh2 group coordinates with titanium by oxygen atom,
gave a clearly higher activity (1.32 3 106 g/mol(Ti)ꢁhꢁatm)
than that of 4c, indicating that the hindrance around
ꢀ
stable over 100 C.
2500
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
TABLE 4 Copolymerization of Ethylene/1-Olefins and Ethylene/NBE with 4a at 50 ꢀCa
d
Comonomer
(mmol)
Time
(min)
Yield
(g)
Incorporation
(mol %)c
Mw
Entrya
Activityb
(104 g/mol)
Mw/Mn
d
1
2
3
4
5
6
7
8
9
Hexene(10)
Hexene(20)
Hexene(40)
Hexene(80)
Octene (20)
Dodecene(40)
Dodecene(80)
NBE(10)
5
5
0.43
0.50
0.21
0.32
3.26
0.80
1.26
0.24
0.18
1.04
1.21
0.52
0.77
2.61
0.64
1.01
0.19
0.14
0.8
1.8
1.8
2.1
2.7
5.9
11.7
4.1
7.5
21.7
22.8
20.6
19.2
11.2
10.2
11.0
14.0
10.2
2.5
2.4
2.6
2.6
2.1
2.2
2.0
2.3
2.9
5
5
15
15
15
15
15
NBE(20)
a
c
Conditions: 50 ꢀC; 1 atm of ethylene; toluene, 50 mL; Al/Ti 5 500; cata-
lyst 4a, 5 mmol.
Determined by 13C NMR.
d
Determined by GPC.
b
106 g/molꢁhꢁatm.
We have tried the synthesis of complex with X as CH2Ph.
The treatment of TiCl4 either with equivalent ligand
(X 5CH2Ph) or with equivalent potassium (or lithium) salt
of the ligand (X 5CH2Ph) gave a mixture. Attempts to purify
it failed. This is totally different from the examples that con-
taining coordination group as a sidearm. In the presence of
MMAO, no polymer was generated when the resulted mix-
ture was used to catalyze the ethylene polymerization at 110
ꢀC.
treated at 50 ꢀC and 500 Al/Ti ratio. NBE is also a good
comonomer and the incorporation ratio also could be
improved by controlling the loading of comonomer. When
20 mmol NBE was used as a comonomer in the presence of
4a/MMAO, 7.5 mol % incorporation ratio was achieved
(entry 9).
Tables 5 and 6 summarized the results of the ethylene/a-ole-
ꢀ
fins copolymerization at 110 C in the presence of 4/MMAO.
The influences of the monomer feed on the activity and
incorporation ratio were first screened in toluene under 1
atm ethylene pressure. As shown in Table 5, the copolymer-
ization proceeded well and the highest activity of 1.52 3 106
g/mol(Ti)ꢁhꢁatm was achieved when 20 mmol 1-octene and
ethylene were copolymerized by 4a/MMAO. Compared with
Whatever catalyst, narrow molecular weight distributions
(Mw/Mn) of the produced PE featured character of single-site
catalyst. The Mw of the resulting polymers decreased with
the increase of polymerization temperature; and, with the
prolonging polymerization time from 2 to 30 min, the molec-
ular weight distribution (Mw/Mn) of the produced PE
changed slightly. A sharp decrease on molecular weight of
the resulted PE from 10.4 3 104 g/mol to 3.6 3 104 g/mol
was observed in the case of improving Al/Ti ratio from 500
to 2000, indicating that chain transfer to aluminum was a
main way of chain termination. 13C NMR analysis exhibited
the polymers are linear. The highest Mw was obtained when
ASPh was introduced as a sidearm group (entry 11). In the
case of 4f, Mw was only 3.83104 g/mol.
6
ꢀ
that at 50 C (2.61 3 10 g/mol(Ti)ꢁhꢁatm, entry 5, Table 4),
the activity of the copolymerization of ethylene/octene
ꢀ
decreased slightly at 110 C (entry 2, Table 5). In both cases,
narrow molecular weight distributions were observed but
molecular weight of the produced copolymer reduced from
11.2 3 104 g/mol to 5.4 3 104 g/mol when changing the
temperature from 50 to 110 ꢀC. The initial concentration of
the comonomer is proportional to the incorporation rate.
Consequently, improved incorporation ratio of 1-octene could
be achieved by increasing the initial amount of octene.
The activity was slightly reduced while increasing the
co-monomer concentration, as reported for other systems.15
As a result, when 40 mmol 1-octene was added, the copoly-
mer (Tm 101.1 ꢀC) was generated in an activity of 0.99 3
106 g/mol(Ti)ꢁhꢁatm and 3.4 mol % incorporation ratio
(entry 3). The highest incorporation ratio of 5.9 mol % with
an activity of 0.74 3 106 g/mol(Ti)ꢁhꢁatm was obtained in
the case of 80 mmol octene being used. Under this condition,
the Tm of the resulting copolymer decreased to 87.8 ꢀC,
probably due to decrease in crystallinity of copolymer with
the incorporation of comonomer (entry 4).
Ethylene Copolymerization with a-Olefins
The copolymerization of ethylene and different comonomers
was screened using 4 activated with MMAO under different
conditions. As shown in Table 4, 4a was first selected to cat-
alyze both the ethylene/a-olefins and ethylene/NBE copoly-
merizations at 50 ꢀC. In the presence of MMAO, 4a showed
high activity for the copolymerization and the incorporation
ratio could be improved by controlling the loading of como-
nomer. For example, the incorporation ratio rise from 0.8 to
2.1 mol % when 80 mmol instead of 20 mmol 1-hexene was
added (entries 1–4). 1-Octene and 1-dedocene also worked
efficiently, and the copolymer was obtained in an activity of
1.0 3 106 g/mol(Ti)ꢁhꢁatm with 11.7 mol % incorporation
ratio when 80 mmol 1-dedocene and ethylene gas was
The structure of the complexes also obviously influenced the
copolymerization. 4d gave low activity even under 5 atm
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503
2501

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
TABLE 5 Copolymerization of Ethylene and 1-Octene Under High Temperaturea
d
Octene
(mmol)
Yield
(g)
Incorp.
ratioc
Mw
Activityb
(104 g/mol)
Mw/Mn
Tm (ꢀC)e
d
Entry
Cat.
1
2
3
4
5
6f
7
8
4a
4a
4a
4a
4b
4d
4e
4f
10
20
40
80
20
20
20
20
1.51
1.90
1.24
0.93
0.35
0.30
0.28
1.52
1.21
1.52
0.99
0.74
0.28
0.05
0.22
1.22
1.1
1.3
3.4
5.9
0.8
2.0
1.5
1.0
7.9
5.4
7.4
5.1
7.7
3.9
5.7
7.0
2.2
2.3
2.3
2.2
2.6
3.9
2.3
2.4
116.0
111.9
101.1
87.7
117.6
117.8
118.2
117.2
a
d
e
f
Toluene, 50 mL; cat. 5 lmol; Al/Ti 5 500; 1 atm ethylene; 15 min; 110 ꢀC.
106 g/molꢁhꢁatm.
Determined by GPC.
Determined by DSC.
b
c
Determined by 13C NMR.
Ethylene pressure: 5 atm.
ethylene atmosphere, and 2.0 mol % incorporation ratio was
obtained. Either 4b or 4e gave lower activities than that of
4a. Similar to the polymerization of ethylene, the introduc-
tion of Bu at C7 position has little impact on the activity as
well as incorporation (entry 8).
presumably deduced from both the stability of the ligands
and their strong coordination to titanium. a-Olefins, such
as 1-octene and 1-octadencene, were proved suitable
comonomer to be incorporated into polyethylene in the
presence of the new complexes at 110 ꢀC. The highest ac-
tivity of the ethylene/1-octadecene copolymerization was
1.89 3 106 g/mol(Ti)ꢁhꢁatm at 110 ꢀC. Increasing the
molar ratio of comonomer leaded to improved incorpora-
tion ratio; and correspondingly, Tm of the produced poly-
mer could be reduced to 87.7 ꢀC. The pendant group X
has great influence on tailoring the structure of polymers
and PPh2 tested to be the best choice. Decreasing the
steric hindrance deteriorated the activity. These results and
the easy modification feature of the complexes are helpful
in developing efficient catalysts used in solution
polymerization.
t
1-Octadecene is also a suitable comonomer at 110 ꢀC. For
example, both 4a and 4f could copolymerize ethylene and 1-
octadecene in an activity above 1.0 3 106 g/mol(Ti)ꢁhꢁatm
with moderate incorporation ratio (entries
1 and 5).
Although similar incorporation ratios of the resulting copoly-
mers could be obtained when complexes 4b–e were applied
as catalysts for the copolymerization, low to moderate
copolymerization activities were observed in the cases
(entries 2–4).
CONCLUSIONS
A
series of titanium complexes bearing phenoxy-amine
were prepared and characterized. In the presence of
MMAO, these titanium complexes displayed unusual ther-
mal stability and single-site ethylene (co)polymerization
behavior under the temperatures of up to 150 ꢀC. The
highest activity of ethylene polymerization was achieved as
5.40 3 106 g/mol(Ti)ꢁhꢁatm at 110 ꢀC. The characters are
ACKNOWLEDGMENTS
The authors thank the financial support from the Natural Scien-
ces Foundation of China (No. 21121062, 21174159), the Sci-
ence and Technology Commission of Shanghai Municipality,
and Chinese Academy of Sciences.
TABLE 6 Copolymerization of Ethylene and 1-Octadecene Under High Temperaturea
d
Yield
(g)
Incorp.
ratioc
Mw
Tm
(ꢀC)e
d
Entry
Cat.
Activityb
(104 g/mol)
Mw/Mn
1
2
3f
4
5
4a
4b
4d
4e
4f
2.36
0.43
0.37
0.31
1.65
1.89
0.34
0.06
0.25
1.32
1.2
0.7
1.3
1.1
1.7
8.3
9.7
8.5
13.5
7.5
2.6
2.5
2.9
2.3
2.7
116.4
117.4
118.8
109.3
115.8
a
d
Toluene, 50 mL; cat., 5 lmol; comonomer, 20 mmol; 1 atm ethylene
Determined by GPC.
e
f
pressure, 15 min, 110 ꢀC.
b
Determined by DSC.
Ethylene pressure: 5 atm.
106 g/molꢁhꢁatm.
c
Determined by 13C NMR.
2502
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
7 Selected examples, see: (a) Q. Wu, Y. Lu, J. Polym. Sci. Part
A: Polym. Chem. 2002, 40, 1421–1425; (b) W. Wang, M. Fujiki,
K. Nomura, J. Am. Chem. Soc. 2005, 127, 4582–4583; (c) H.
Zhang, K. Nomura, J. Am. Chem. Soc. 2005, 127, 9364–9365;
(d) K. Nomura, K. Itagaki, M. Fujiki, Macromolecules 2005, 38,
2053–2055; (e) K. Nomura, W. Wang, M. Fujiki, J. Liu, Chem.
Commun. 2006, 25, 2659–2661; (f) M. Srebro, Ł. Pie¸kosꢀ, T.-J.
Kim, M. Cheong, M.-A. Ok, S. O. Kang, A. Michalak, Organome-
tallics 2010, 29, 5341–5352; (g) K. Nomura, N. Suzuki, D.-H.
Kim, H. J. Kim, Macromol. React. Eng. 2012, 6, 351–356.
REFERENCES AND NOTES
1 (a) B. T. Huang, W. Chen, Metallocene Catalysts and Their
Olefin Polymers; Chemical Engineering Press: Beijing, 2000; (b)
O. B. de Oliveira, S. T. Brandao, A. J. D. de Freitas, da E. P.
Silva, S. M. P. Meneghetti, M. R. Meneghetti, Polym. Int. 2008,
57, 1012–1016; (c) C. S. Popeney, A. L. Rheingold, Z. Guan,
Organometallics 2009, 28, 4452–4463.
2 (a) A. Yano, M. Sone, S. Yamada, S. Hasegawa, M. Sato, A.
Akimoto, J. Mol. Catal. A: Chem. 2000, 156, 133–141; (b) S.
Hasegawa, M. Sone, M. Tanabiki, M. Sato, A. Yano, J. Polym.
Sci. Part A: Polym. Chem. 2000, 38, 4641–4648; (c) A. S. Ionkin,
W. J. Marshall, D. J. Adelman, B. B. Fones, B. M. Fish, M. F.
Schiffhauer, Organometallics 2006, 25, 2978–2992; (d) K.-S.
8 Selected examples, see: (a) S. Fokken, T. P. Spaniol, J. Okuda,
€
F. G. Sernetz, R. Mulhaupt, Organometallics 1997, 16, 4240–
€
4242; (b) F. G. Sernetz, R. Mulhaupt, S. Fokken, J. Okuda, Macro-
molecules 1997, 30, 1562–1569; (c) E. Y. Tshuva, I. Goldberg, M.
Kol, H. Weitman, Z. Goldschmidt, Chem. Commun. 2000, 379–
380; (d) E. Y. Tshuva, I. Goldberg, M. Kol, J. Am. Chem. Soc.
2000, 122, 10706–10707; (e) E. Y. Tshuva, I. Goldberg, M. Kol, Z.
Goldschmidt, Organometallics 2001, 20, 3017–3028; (f) E. Y.
Tshuva, I. Goldberg, M. Kol, Z. Goldschmidt, Chem. Commun.
2001, 2120–2121; (g) E. Y. Tshuva, S. Groysman, I. Goldberg, M.
Kol, Z. Goldschmidt, Organometallics 2002, 21, 662–670.
€
Son, F. Joge, R. M. Waymouth, Macromolecules 2008, 41,
9663–9668; (e) T.-J. Kim, S.-K. Kim, J. S. Hahn, M.-A. Ok, J. H.
Song, D.-H. Shin, J. Ko, M. Cheong, J. Kim, H. Won, M.
Mitoraj, M. Srebro, A. Michalak, S. O. Kang, Macromolecules
2009, 42, 6932–6943.
3 (a) G. J. P. Britovsek, V. C. Gibson, D. F. Wass, Angew.
Chem. Int. Ed. Engl. 1999, 38, 428–447; (b) S. D. Ittel, L. K.
Johnson, M. Brookhart, Chem. Rev. 2000, 100, 1169–1203; (c)
S. Mecking, Angew. Chem. Int. Ed. Engl. 2001, 40, 534–540; (d)
V. C. Gibson, S. K. Spitzmesser, Chem. Rev. 2003, 103, 283–
315; (e) H. Makio, T. Fujita, Acc. Chem. Res. 2009, 42, 1532–
1544; (f) B. M. Boardman, G. C. Bazan, Acc. Chem. Res. 2009,
42, 1597–1606; (g) A. Nakamura, S. Ito, K. Nozaki, Chem. Rev.
2009, 109, 5215–5244; (h) S. Budagumpi, K.-H. Kim, I. Kim.
Coord. Chem. Rev. 2011, 255, 2785–2809; (i) J.-Q. Wu, Y.-S. Li,
Coord. Chem. Rev. 2011, 255, 2303–2314; (j) N. Nakata, T. Toda,
A. Ishii, Polym. Chem. 2011, 2, 1597–1610; (k) C. Redshaw, Y.
Tang, Chem. Soc. Rev. 2012, 41, 4484–4510.
9 Selected examples, see: (a) X.-F. Li, Y.-G. Li, Y.-S. Li, Y.-X.
Chen, N.-H. Hu, Organometallics 2005, 24, 2502–2510; (b) L.-M.
Tang, Y.-Q. Duan, L. Pan, Y.-S. Li, J. Polym. Sci. Part A: Polym.
Chem. 2005, 43, 1681–1689; (c) L. Pan, W.-P. Ye, J.-Y. Liu, M.
Hong, Y.-S. Li, Macromolecules 2008, 41, 2981–2983; (d) Y.-Y.
Long, Y.-X. Wang, J.-Y. Liu, Y.-S. Li, J. Polym. Sci. Part A:
Polym. Chem. 2012, 50, 638–648.
10 (a) X. Li, Z. Hou, Macromolecules 2010, 43, 8904–8909; (b) K.
A. Frazier, R. D. Froese, Y. He, J. Klosin, C. N. Theriault, P. C.
Vosejpka, Z. Zhou, Organometallics 2011, 30, 3318–3329; (c) F.
Marchetti, G. Pampaloni, Y. Patil, A. M. Raspolli Galletti, F.
Renili, S. Zacchini, Organometallics 2011, 30, 1682–1688; (d) F.
Guo, M. Nishiura, H. Koshino, Z. Hou, Macromolecules 2011,
44, 6335–6344; (e) L. Pan, K. Zhang, M. Nishiura, Z. Hou,
Angew. Chem. Int. Ed. Engl. 2011, 50, 12012–12015; (f) A.-Q.
Jia, J.-Q. Wang, P. Hu, G.-X. Jin, Dalton Trans. 2011, 40, 7730–
7736; (g) P. Hu, J.-Q. Wang, F. Wang, G.-X. Jin, Chem. Eur. J.
2011, 17, 8576–8583; (h) P. Hu, Y.-L. Qiao, J.-Q. Wang, G.-X.
Jin, Organometallics 2012, 31, 3241–3247.
4 Selected examples, see: (a) L. K. Johnson, C. M. Killian, M.
Brookhart, J. Am. Chem. Soc. 1995, 117, 6414–6415; (b) D. H.
Camacho, E. V. Salo, J. W. Ziller, and Z. Guan, Angew. Chem.
Int. Ed. Engl. 2004, 43, 1821–1825; (c) G. Noell, J. C. Roder, S.
Dechert, H. Pritzkow, L. Bolk, S. Mecking, F. Meyer, Adv. Synth.
Catal. 2006, 348, 887–897; (d) C. S. Popeney, C. M. Levins, Z.
Guan, Organometallics 2011, 30, 2432–2452.
€
€
5 Selected examples, see: (a) T. R. Younkin, E. F. Connor, J. I.
Henderson, S. K. Friedrich, R. H. Grubbs, D. A. Bansleben, Sci-
ence 2000, 287, 460–462; (b) J. Saito, M. Mitani, J. Mohri, Y.
Yoshida, S. Mastui, S. Ishii, S. Kojoh, N. Kashiwa, T. Fujita,
Angew. Chem. Int. Ed. Engl. 2001, 40, 2918–2920; (c) J. Tian, P.
D. Hustad, G. W. Coate, J. Am. Chem. Soc. 2001, 123, 5134–
5135; (d) S. Matsui, M. Mitani, J. Saito, Y. Tohi,H. Makio, N.
Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H.
Tanaka, N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 2001, 123,
6847–6856; (e) M. Mitani, J. Mohri, Y. Yoshida, J. Saito, S. Ishii,
K. Tsuru, S. Matsui, R. Furuyama,T. Nakano, H. Tanaka, S.
Kojoh, T. Mastugi,N. Kashiwa, T. Fujita, J. Am. Chem. Soc.
2002, 124, 3327–3336; (f) M. Mitani, R. Furuyama, J. Mohri, J.
Saito, S. Ishill, H. Terao, N. Kashiwa, T. Fujita, J. Am. Chem.
Soc. 2002, 124, 7888–7889; (g) J.-Q. Wu, L. Pan, S.-R. Liu, L.-P.
He, Y.-S. Li, J. Polym. Sci. Part A: Polym. Chem. 2009, 47,
3573–3582; (h) Y. Patil, A. M. Raspolli Galletti, G. Silly, B. Ame-
duri, J. Fluorine. Chem. 2011, 132, 1207–1212; (i) N. A. Kolhat-
kar, A. M. Monfette, S. Lin, M. J. Miri, J. Poly. Sci. Part A:
Polym. Chem. 2012, 50, 986–995.
11 (a) R. Eaves, S. Parkin, F. T. Ladipo, Inorg. Chem. 2007, 46,
9495–9502; (b) S. Zhang, W.-H. Sun, T. Xiao, X. Hao, Organo-
metallics 2010, 29, 1168–1173; (c) P. P. Fontaine, J. Klosin, N. T.
McDougal, Organometallics 2012, 31, 624426251.
12 (a) W.-Q. Hu, X.-L. Sun, C. Wang, Y. Tang, L.-P. Shi, W. Xia,
J. Sun, H.-L. Dai, X.-X. Li, X.-L. Yao, X.-R. Wang, Organometal-
lics 2004, 23, 1684–1688; (b) C. Wang, X.-L. Sun, Y.-H. Guo, Y.
Gao, B. Liu, Z. Ma, W. Xia, L.-P. Shi, Y. Tang, Macromol. Rapid.
Commun. 2005, 26, 1609–1614; (c) C. Wang, Z. Ma, X.-L. Sun,
Y. Gao, Y.-H. Guo, Y. Tang, L.-P. Shi, Organometallics 2006, 25,
3259–3266; (d) M.-L. Gao, C. Wang, X.-L. Sun, C.-T. Qian, Z.
Ma, S.-Z. Bu, Y. Tang, Z. Xie, Macromol. Rapid Commun. 2007,
28, 1511–1516; (e) X.-H. Yang, C.-R. Liu, C. Wang, X.-L. Sun, Y.-
H. Guo, X.-K. Wang, Z. Wang, Z. Xie, Y. Tang, Angew. Chem.
Int. Ed. Engl. 2009, 48, 8009–8102.
13 S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsu-
kawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka,
N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 2001, 123, 6847–6856.
ꢀ
ꢀ
14 B. Cordero, V. Gomez, A. E. Platero-Prats, M. Reves, J.
ꢀ
ꢀ
Echeverrıa, E. Cremades, F. Barragan, S. Alvarez, Dalton Trans.
6 Selected examples, see: (a) B. L. Small, M. Brookhart, A. M.
A. Bennett, J. Am. Chem. Soc. 1998, 120, 4049–4050; (b) G. J.
P. Britovsek, V. C. Gibson, B. S. Kimberley, P. J. Maddox, S. J.
McTavish, G. A. Solan, A. J. P. White, D. Williamsa J. Chem.
2008, 2832–2838.
15 (a) J. C. W. Chien, T. Nozaki, J. Polym. Sci. Part A: Polym.
Chem. 1993, 31, 227–237; (b) P. Kumkaew, L. Wu, P. Praserth-
dam, S. E. Wanke, Polymer 2003, 44, 4791–4803; (c) K. Heiland,
W. Kaminsky, Makromol. Chem. 1992, 193, 601–610.
€
Commun. 1998, 849–850; (c) C. Gorl, T. Englmann, H. G. Alt,
Appl. Catal. A Gen. 2011, 403, 25–35.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 2495–2503
2503