terpolymerization of propylene oxide, cyclohexene oxide ... · 1 Supporting Information...
Transcript of terpolymerization of propylene oxide, cyclohexene oxide ... · 1 Supporting Information...
1
Supporting Information
Structure-induced catalytic activity of Co-Zn double-metal cyanide complexes for
terpolymerization of propylene oxide, cyclohexene oxide and CO2
Joby Sebastian†, ‡, Darbha Srinivas†, ‡, *
† Catalysis Division, CSIR-National Chemical Laboratory, Pune-411 008, India.
‡ Academy of Scientific and Innovative Research (AcSIR), New Delhi- 110 001, India.
E-mail: [email protected], Tel: +91 20 2590 2018, Fax: +91 20 2590 2633.
___________________________________________________________________________
S1. 1H NMR spectrum of PCHC.
S2. 1H NMR spectrum of PPC.
S3. 1H NMR spectra of all polycarbonates.
S4. 13C inverse gated NMR of the copolymers and terpolymer in the CH and CH2
regions of PPC.
S5. 13C inverse gated NMR of the copolymers and terpolymer in the CH3 region.
S6. Thermograms of PPC, PCHC and terpolymer.
S7. FTIR of Co-Zn DMC catalysts.
S8. DRIFT spectrum of adsorbed pyridine on DMC-II showing bands due to
Lewis acid sites..
S9. NH3-TPD of DMC-II.
S10 Powder XRD of PCHC and terpolymer produced using DMC-II catalyst.
S11 SEM images of PCHC and terpolymer produced over DMC-II
S12. 1H NMR spectrum of crude terpolymer synthesised over DMC-II.
S13. Reaction time verses reactor pressure at different reaction conditions.
S14. PXRD patterns of fresh and spent DMC-II catalyst.
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015
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5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
a
b
d, d'
c, c'
OC
O
O O Oa b
c
d'
c'
dm n
S1. 1H NMR spectrum of purified PCHC.
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S2. 1H NMR spectrum of purified PPC.
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)
a
b
c
d,e fg h i
j
OO O
O
O
O
Oa
b
c
d
g
f
eh,i
j
4
S3. 1H NMR spectra of PPC, PCHC, PPC + PCHC physical blend and PO-CHO-CO2
terpolymer.
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)
PPC
PCHC
PPC + PCHC
Terpolymer
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S4. Inverse-gated 13C NMR of the polycarbonates in the CH (72.07 and 72.30 ppm) and CH2
(68.93 ppm) regions of PPC. The terpolymer spectrum appeared as broad peaks without
considerable splits as in the blend and PPC. It also clear that there is a change in tacticity
pattern for the terpolymer as compared to PPC (reversal of intensity distribution of 72.30
ppm in terpolymer as compared to PPC).
PPC
PCHC
PPC + PCHC
Terpolymer
86 84 82 80 78 76 74 72 70 68 66 64Chemical Shift (ppm)
72.3
072
.07
68.9
3
6
S5. 13C inverse gated NMR of the polycarbonates in the CH3 region (16.17 and 16.63 ppm) of
PPC and CH2 region (22.8 and 29.64 ppm) of PCHC. No major difference was observed in
the CH3 region of terpolymer as compared to PPC, but the peaks appeared as merged in case
of CH2 regions of terpolymer as compared to PCHC.
PPC
PCHC
PPC + PCHC
Terpolymer
34 32 30 28 26 24 22 20 18 16 14Chemical Shift (ppm)
29.6
429
.49 23
.03
22.8
8
16.6
316
.17
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S6. Thermograms of PPC, PCHC and terpolymer synthesized over DMC-II.
100 200 300 400 5000
50
1000
50
1000
50
100
Temperature (oC)
Weig
ht (%
)
PPC
PCHC
Terpolymer
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2350 2300 2250 2200 2150 2100 2050
2224
2208
2166 21
50
Tran
smitt
ance
(%)
Wavenumber (cm-1)
2191
(b)
2222
217421
92
(a)
S7. FTIR of (a) DMC-I and (b) DMC-II catalysts. Band assignments are given below.
Band position (cm-1) Band assignment3590 -OH stretch2955 -C-H stretch2191 -CN stretch1614 -OH bending (H2O)1465 -CH scissoring1370 -OH bending (tert-butanol)1190 3°-C-O stretch475 Co-CN stretch
4000 3500 3000 2500 2000 1500 1000 500
475
1190
1370
1465
3590
1614
2955 Tr
ansm
ittan
ce (%
)
Wavenumber (cm-1)
(b) 2191
(a)
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S8. DRIFT spectra of adsorbed pyridine on DMC-II showing bands due to Lewis acid sites.
1650 1600 1550 1500 1450 1400
Abso
rban
ce (a
.u)
Wavenumber (cm-1)
1608
1619
1576
1493
1452
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S9. NH3-TPD of DMC-II.
100 120 140 160 180 200
NH
3 des
orbe
d (m
l/g)
Temperature (oC)
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S10. PXRD of PCHC and terpolymer produced using DMC-II catalyst.
10 20 30 40 50 60 70
Inten
sity (
a.u)
2 (degree)
PCHC
10 20 30 40 50
Inte
nsity
(a.u
)2 (degree)
Terpolymer
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PCHC Terpolymer
S11. SEM images of PCHC and PO-CHO-CO2 terpolymer produced over DMC-II.
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S12. 1H NMR spectrum of crude terpolymer synthesised over DMC-II. The assigned peaks correspond to cyclic propylene carbonate (PC).
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)
4.92 4.85
4.81
4.60 4.56
4.52 4.074.03
4.00
1.52 1.49
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S13. Reaction time verses reactor pressure at different reaction conditionsusing DMC-II as catalyst. (a) effect of temperature, (b) effect of CO2 pressure, (c) effect of catalyst quantity
and (d) effect of % PO in reactant epoxide mixture.
0 2 4 6 8 10280
320
360
400
440
Re
acto
r pre
ssur
e (ps
i)
Reaction time (h)
95 oC 85 oC 75 oC
(a)
0 2 4 6 8 100
100
200
300
400
Reac
tor P
ress
ure (
Psi)
Reaction time (h)
20 bar 10 bar 30 bar
(b)
0 2 4 6 8 10
250
300
350
400
450
Reac
tor p
ress
ure (
psig
)
Reaction time (h)
0.083 g 0.113 g 0.226 g
(c)
0 2 4 6 8 10
225
300
375
450
525
Reac
tor p
ress
ure (
psi)
Reaction time (h)
80% 66% 57% 50% 43% 33% 20%
(d)
15
10 20 30 40 50
Inte
nsity
(a.u
)
2 (degree)
Recycled
Fresh
S14. PXRD patterns of fresh and spent DMC-II catalyst. Reaction conditions: CHO = 5.6 g, PO = 3.5 g, CHO : PO molar ratio = 1:1, catalyst = 0.226 g, toluene = 8.7 g, pCO2 = 30 bar,
reaction time = 11 h, reaction temperature = 85°C.