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Electronic supporting information

Carbocationic polymerization of isoprene using cumyl initiators: progress in

understanding side reactions

Samira Ouardada, Anne-Laure Wirotiusa, Sergei V. Kostjukb, François Ganachaudc, Frédéric

Perucha

a Univ. Bordeaux, CNRS, INP Bordeaux, LCPO, UMR 5629, F-33600 Pessac, France.

b Research Institute for Physical Chemical Problems of the Belarusian State University,

220030 Minsk, Belarus

c Univ Lyon, CNRS, INSA-Lyon, IMP, UMR5223, F-69621 Villeurbanne, France

Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2015

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OCH3

b c

d

a

b c

a e

b d

a

e c

CH2Cl2

b c

d

a b

c’

e

a e

b

c, d

CHCl3

Cl

b c

d

a

b’ c’

a

b, b’ d

a

c, c’ CH2Cl2

Figure S1: 1H NMR spectra of cumyl chloride, cumyl ether and α-methylstyrene. (from top to bottom)

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Figure S2: Maldi-TOF MS spectra of oligoisoprenes obtained by the system

IP/CumylCl/B(C6F5)3/dtBP at 20°C.

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C H2 C C

H C

H2 C

H2 C C C

H

CH3 H2 C

H2 C C

H2 C

H C C

H C

CH3

CH H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5

b2* c2* c2'* b2

c2 c2'

c3

d3 b3

e4 c4

d4

b5 f5 b5'

d5 f3f1 n

m p

CH3

{b2}

{d4, d5}

{c2*}

Ar

Ar

{b2*}

{a2}

{d3}

{c2’}

{c2}

{a4}

Figure S3: Typical HSQC NMR spectrum of the polyisoprene obtained with

IP/CumylOCH3/TiCl4/dtBP system.

500 1000 1500 2000

150/1/2 and [IP] = 2,4 M

299/1/2 and [IP] = 4,8 M

299/1/2 and [IP] = 2,4 M

Time (s)

Figure S4: SEC spectra of polyisoprenes obtained varying IP/CumylOCH3/TiCl4 ratio.

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b2

a2

c2, c2’

a1Ar

b3

d3

d5

a3 a4

d4 b5 e4

C H2 C C

H C

H2 C

H2 C C C

H

CH3

H2 C

H2 C C

H2 C

H C C

H C

CH3

CH

H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5

b2* c2* c2'* b2

c2 c2'

c3

d3

b3

e4c4

d4

b5 f5 b5' d5 f3f1 n

m p

CH3

a2*

Saturated fragments

b2*

c2*

Ar

CH-X and CH2-X

Figure S5: 1H NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP

systems.

b2

f2

C2 t-q

C2’ t-q

c2 q-q

C2 t-t

a1 a2

Ar

d4, d5d3b3

a3

c3 3-c2

b2*

f1

a4

ci s ci s

e4

a1 a1

a2*

a2

a3

a4 a5

b2*

c2*

c2'*

b2c2

c2'

c3

d3 b3

e4

d4

b5

f5

b5'

d5f3 f1 c4n  

f2*

Ar

Ar

c2*

a2*

ALIPHATIC PART

OLEFINIC PART

Figure S6: JMOD NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.

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C H2 C C

H C

H2 C

H2 C C C

H

CH3 H2 C

H2 C C

H2 C

H C C

H C

CH3

CH H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5

b2* c2* c2'* b2

c2 c2'

c3

d3 b3

e4 c4

d4

b5 f5 b5'

d5 f3f1 n

m p

CH3

{b2,c2/c2’} {b2,a2}

{b2*,c2*/c2’*}

Ar

Ar

{b2*,a2*} {c2/c2’,a2}

Artefacts

Figure S7: TOCSY NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.

C H2 C C

H C

H2 C

H2 C C C

H

CH3 H2 C

H2 C C

H2 C

H C C

H C

CH3

CH H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5

b2* c2* c2'* b2

c2 c2'

c3

d3 b3

e4 c4

d4

b5 f5 b5'

d5 f3f1 n

m p

CH3

{b2} {d4, d5}

{c2*}

Ar

Ar

{b2*}

{a2}

{b3}

Artefacts

{a1}

Figure S8: NOESY NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.

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C H2 C C

H C

H2 C

H2 C C C

H

CH3 H2 C

H2 C C

H2 C

H C C

H C

CH3

CH H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5

b2* c2* c2'* b2

c2 c2'

c3

d3 b3

e4 c4

d4

b5 f5 b5'

d5 f3f1 n

m p

CH3

{b2,c2/c2’}

{b3,d3}

{b2*,c2*/c2’*}

Ar

Ar

{b2*,a2*}

{c2/c2’,a2}

Artefacts

Figure S9: COSY NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.

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C H2 C C

H C

H2 C

H2 C C C

H

CH3 H2 C

H2 C C

H2 C

H C C

H C

CH3

CH H2C

C H

C H2C CH3

CH2

CH3CH3

CH3

a1

a1

a2* a2 a3

a4

a5 b2*

c2* c2'* b2 c2 c2' c3

d3 b3

e4 c 4

d4

b5 f5

b5' d5

f3f1 n

m p

CH3



X

a6 b6

c6'c6

Figure S10: HMBC NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.