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  • 1

    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

  • 2

    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.

  • 5

    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.

  • 6

    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.

  • 7

    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.

  • 8

    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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