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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)
3
Figure S2: Maldi-TOF MS spectra of oligoisoprenes obtained by the system
IP/CumylCl/B(C6F5)3/dtBP at 20°C.
4
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.
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