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: d.srinivas@ncl.res.in, 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

2

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.

3

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

5

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

7

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

8

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)

9

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

10

S9. NH3-TPD of DMC-II.

100 120 140 160 180 200

NH

3 des

orbe

d (m

l/g)

Temperature (oC)

11

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

12

PCHC Terpolymer

S11. SEM images of PCHC and PO-CHO-CO2 terpolymer produced over DMC-II.

13

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.