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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
bc
d
a
bc
ae
b d
a
ec
CH2Cl2
bc
d
ab
c’
e
ae
b
c, d
CHCl3
Cl
bc
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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CH2C C
HC
H2C
H2C C C
H
CH3H2C
H2C C
H2C
HC C
HC
CH3
CHH2C
CH
CH2C CH3
CH2
CH3CH3
CH3
a1
a1
a2* a2 a3
a4
a5
b2*c2* c2'* b2
c2 c2'
c3
d3b3
e4c4
d4
b5f5 b5'
d5f3f1 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
a3a4
d4b5 e4
CH2C C
HC
H2C
H2C C C
H
CH3
H2C
H2C C
H2C
HC C
HC
CH3
CH
H2C
CH
CH2C 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' d5f3f1 n
m p
CH3
a2*
Saturatedfragments
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
C2t-t
a1 a2
Ar
d4, d5d3b3
a3
c33-c2
b2*
f1
a4
cis cis
e4
a1 a1
a2*
a2
a3
a4 a5
b2*
c2*
c2'*
b2c2
c2'
c3
d3b3
e4
d4
b5
f5
b5'
d5f3f1 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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CH2C C
HC
H2C
H2C C C
H
CH3 H2C
H2C C
H2C
HC C
HC
CH3
CHH2C
CH
CH2C CH3
CH2
CH3CH3
CH3
a1
a1
a2* a2 a3
a4
a5
b2*c2* c2'* b2
c2 c2'
c3
d3b3
e4c4
d4
b5f5 b5'
d5f3f1 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.
CH2C C
HC
H2C
H2C C C
H
CH3 H2C
H2C C
H2C
HC C
HC
CH3
CHH2C
CH
CH2C CH3
CH2
CH3CH3
CH3
a1
a1
a2* a2 a3
a4
a5
b2*c2* c2'* b2
c2 c2'
c3
d3b3
e4c4
d4
b5f5 b5'
d5f3f1 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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CH2C C
HC
H2C
H2C C C
H
CH3 H2C
H2C C
H2C
HC C
HC
CH3
CHH2C
CH
CH2C CH3
CH2
CH3CH3
CH3
a1
a1
a2* a2 a3
a4
a5
b2*c2* c2'* b2
c2 c2'
c3
d3b3
e4c4
d4
b5f5 b5'
d5f3f1 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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CH2C C
HC
H2C
H2C C C
H
CH3H2C
H2C C
H2C
HC C
HC
CH3
CHH2C
CH
CH2C CH3
CH2
CH3CH3
CH3
a1
a1
a2* a2 a3
a4
a5b2*
c2* c2'* b2c2 c2' c3
d3b3
e4c4
d4
b5f5
b5' d5
f3f1 n
m p
CH3
X
a6b6
c6'c6
Figure S10: HMBC NMR spectrum of the polyisoprene obtained with IP/cumylOCH3/TiCl4/dtBP system.
