Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Supplementary Material
A solid homogeneous zirconocene catalyst
from Cp2ZrCl2 supported on porous polymer
particles
Lei Jinhua1.2, Li Dongliang1.2, Wang Honghua1 Wang Zhuqian1 Zhou Guangyuan1*
(1. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences
130022 e-mail: gyzhou@ciac.jl.cn；2.Graduate University of Chinese Academy
of Sciences, Beijing 100049, China)
Table of contents
General methods………………………………………………………………………….S2
Synthesis of P, P1 and PSD………………………………………………………………S3
Synthesis of Polymer supported catalysts………………………………………………S4
Ethylene polymerization…………………………………………………………………S5
Table 1 Standard recipe of the seeded polymerization…………………………………S6
Figure S1. FT-IR spectra of the porous particles………………………………………S7
Figure S2. DSC curves of polyethylene…………………………………………………S8
Figure S3. GPC results of polyethylene…………………………………………………S9
Figure S4. FT-IR spectra of polyethylene………………………………………………S10
Figure S5. XRD spectra of polyethylene………………………………………………S11
Figure S6. 13C-NMR spectra of polyethylene……………………………………………S12
References………………………………………………………………………………S13
S1
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
General methods:
Materials:
All reagents were used without further purification unless otherwise are specified.
Styrene (analytical reagent; Beijing Reagents Factory) and 1,4-divinylbenzene (DVB;
analytical reagent; Tianjin Reagents Factory) were washed with a 10% aqueous sodium
hydroxide solution and water, dried over anhydrous magnesium sulfate, and distilled in
vacuum.
Acrylonitrile (Chemical pure, Shanghai Reagent Factory) was distilled in vacuum.
Bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2) was purchased from Aldrich.
MMAO in heptane (18 wt %) was from Ethyl Corp.
Azobis(isobutylronitrile) (AIBN, Beijing Chemical Factory) and benzoyl peroxide (BPO,
Beijing Chemical Factory) were recrystallized in methanol before use.
Measurements.
1. The morphology and porosity of the porous particles were characterized using a
scanning electron microscope (SEM, XL30ESEM-FEG FEL), and
Brunauer–Emmett–Teller (BET, ASAP2020 Micromeritics) isotherm of
sorption/desorption of nitrogen, respectively.
2. The phase morphological characteristics of the samples were investigated by
means of TEM performing on a JEM1011 microscopy operating at 100kV. Prior
to the examination, ultrathin sections were cut using an ultramicrotome and they
were stained in RuO4 vapor for 24h.
3. The Zr and Al contents of the supported catalyst were determined by inductively
coupled plasma atomic emission spectroscopy (ICP-AES)
4. The N content of the polymer beads was determined by elemental analysis.
5. Molecular weights were measured by gel permeation chromatography (GPC)
6. Thermal analysis: Thermal analyses were preformed on a PERKIN-ELMER 7 Series
Thermal Analysis System(DSC), the analyses were made under constant stream of
nitrogen with a heating and cooling rate 10 oC/min. The relative crystallinity of
samples was calculated according to equation 1:
Χc (%) = (ΔHm/ΔHm*)×100 (1)
Where Xc is the percent crystallinity, ΔHm is the enthalpy of melting of the sample,
and ΔHm* is the heat of melting of 100% crystalline PE. The value of ΔHm* used in
the calculation is 290 J/g.
7. NMR analysis: 13C-NMR spectra were recorded on a Bruker DPX-300 Sample
8. FT-IR analysis: FT-IR spectra were recorded on a Bruker Vertex 70FTIR
9.
Powder X-ray diffraction (PXRD) patterns were obtained through a Siemens D5005
diffractometer with. Cu target Kα-ray
S2
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Preparation of monodisperse cyano-functionalized porous poly(St-co-DVB-co-AN)
microspheres (P, P1 and PSD)
we employed seeded polymerization to produce monodisperse cyano-functionalized
porous polymeric beads (PSDA for short)1. Firstly, polystyrene (PS) seed particles,
prepared by dispersion polymerization, were dispersed in 0.25 wt% SLS water/EtOH
(5/1, g/g) solution (SE solution) using a 250 ml four-necked round bottom flask
equipped with a reflux condenser, nitrogen inlet apparatus and a mechanical stirrer.
The CD emulsions in the SE solution were poured into the seed dispersion. The
stirring speed and temperature were fixed at 200 rpm and 30℃ throughout the
swelling process. After complete disappearance of the CD droplets, the second
monomer mixture (St/DVB/AN), BPO and diluent (toluene/heptane) were emulsified
and added into the reactor for another 12 h of swelling. The swollen particles were
stabilized with a 5% PVP K-30 aqueous solution, and then polymerized at 80℃ for
12 h. The resulting particles were washed repeatedly using water and ethanol.
Subsequently, the soxhlet extraction was followed by methylene chloride for 24 h to
eliminate the seed particle and porogen. The standard recipe for seeded
polymerization of cyano-functionalized porous polymeric microspheres is shown in
Table 1.
S3
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Preparation of polymer supported catalysts
MMAO pretreatment of supports and reaction between Cp2ZrCl2 and supports were
conducted under nitrogen atmosphere in a specially designed flask with a magnetic
stirring bar in it. About 1g of support was first suspended in 40 ml of toluene with
vigorous stirring. 17.76ml of MMAO heptane solution(c(Al)=1 mol/L) was added to
the suspended support mixture and stirred for 12h at 50℃. The liquid phase was
removed and the solid was washed with 20 ml of toluene at room temperature for four
times. Then the MAO treated support was suspended again in 40 ml of toluene,
17.76ml of catalyst toluene solution (c(Zr)=0.02 mol/L) was added and stirred at 50℃
for 12h. Finally the supported catalyst was obtained by removing the liquid phase,
washed four times with 20 ml of toluene per time, dried under vacuum at room
temperature, and recovered as free flowing powder. The zirconium (Zr) content of
supported catalyst measured by inductively coupled plasma atomic emission
spectroscopy was about 0.204 mmolZr/g beads.
S4
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Ethylene polymerization
The ethylene polymerization was carried out in stainless steel autoclave reactor. After
the reactor was heated and evacuated for about 30 min, the catalysts, toluene, and
MMAO (Al/Zr=600) were led into the reactor in succession. Polymerization started
with the introduction of ethylene (5 bar). After the required reaction time, the
polymerization was stopped by rapid depressurization of the reactor and quenching
with acidified (HCl) ethanol. The reaction mixture was precipitated in acidified
ethanol over 5h, then filtered, washed with ethanol and dried in a vacuum oven
overnight.
S5
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Table 1 Standard recipe of the seeded polymerization
Stage
Ingredient
P
P1
PSD
Seed dispersion
PS seed particles (g)
SE solutiona (g)
1-CD (g)
SE solution (g)
St (g)
DVB (g)
AN (g)
T (g)
BPO (g)
SE solution (g)
2.5wt%PVP solution (g)
0.5
25
0.5
25
2
6
2
10
0.1
40
50
0.5
25
0.5
25
7
1
2
10
0.1
40
50
0.5
25
0.5
25
4
6
0
10
0.1
40
50
CD swelling
The second monomer
swelling
Stabilization
Polymerization condition: 80℃ , 12 h.
a
0.25 wt% of SLS in EtOH/water (1/5, w/w) solution.
S6
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Transmittance
(a)
(b)
4000
3500
3000
1500
2000
2500
1000
500
-1
Wavenumber (cm )
Figure S1. FT-IR spectra of the porous particles without functional group
(a),cyano-functional groups (b).
S7
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
50
Heat Flow Endo (mW)
45
PE090319b
PE090401a
PE090331
40
35
30
25
20
15
60
80
100
120
140
o
Temperature ( C)
Figure S2. DSC curves of polyethylene: (red), PE090331; (black), PE090401a; and
(blue), PE090319b.
S8
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
0.7
PE090319b
PE090401a
PE090331
0.6
dw/dlogM
0.5
0.4
0.3
0.2
0.1
0.0
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
log M
Figure S3. GPC results of polyethylene: (red), PE090331; (black), PE090401a; and
(blue), PE090319b.
S9
908
1367
1301
1636
1895
2018
2659
4000
3500
2918
2849
PE090319b
PE090401a
PE090331
1472
719
Baseline drift
Transmittance
3603
2343
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Figure S4. FT-IR spectra of polyethylene: (red), PE090331; (black), PE090401a; and
(blue), PE090319b.
S10
Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
Intensity
PE090319b
PE090401a
PE090331
10
20
30
40
50
60
2(degree)
Figure S5. XRD spectra of polyethylene: (red), PE090331; (black), PE090401a; and
(blue), PE090319b.
S11
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Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
PE090319b
PE090331
175
150
125
100
75
50
25
ppm
0
Figure S6. 13C-NMR spectra of polyethylene: (red), PE090331; and (blue), PE090319b.
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Supplementary Material (ESI) for Journal of Polymer Science Part A: Polymer Chemistry
This journal is (c) John Wiley & Sons, Inc. 2010
References
1.
J. B. Nam, J. H. Ryu, J. W. Kim, I. S. Chang and K. D. Suh, Polymer, 2005,
46, 8956-8963.
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