Table 1 Polymerization results by different LPsa.

From: Dual-initiating and living frustrated Lewis pairs: expeditious synthesis of biobased thermoplastic elastomers

Run

LB

LA

M

[M]:[LA]:[LB]

Solvent

Time (min)

Conv.b (%)

Mn (Mw)c (kg·mol−1)

Ðc

I*d (%)

1

μHex[P(NIiPr)Ph]2

Al(C6F5)3

MMA

400:4:1

TOL

0.3

100

52.9

1.20

76

2

μHex[P(NIiPr)Ph]2

AlMe3

MMA

400:4:1

TOL

1440

71.6

n.d

n.d

n.d

3

μHex[P(NIiPr)Ph]2

(BHT)AliBu2

MMA

400:4:1

TOL

0.5

100

52.2

1.37

77

4

μHex[P(NIiPr)Ph]2

(BHT)2AliBu

MMA

400:4:1

TOL

540

100

39.6

1.28

103

5

μHex[P(NIiPr)Ph]2

(BHT)2AlMe

MMA

400:4:1

TOL

3

100

41.7

1.20

97

6

μEt[P(NIiPr)Ph]2

(BHT)2AlMe

MMA

400:4:1

TOL

10

100

59.1

1.28

69

7

μPr[P(NIiPr)Ph]2

(BHT)2AlMe

MMA

400:4:1

TOL

4

100

39.2

1.22

103

8

μBu[P(NIiPr)Ph]2

(BHT)2AlMe

MMA

400:4:1

TOL

4

100

41.0

1.20

99

9

DPPE

(BHT)2AlMe

MMA

400:4:1

TOL

30

100

434

1.49

9

10

DPPP

(BHT)2AlMe

MMA

400:4:1

TOL

30

100

271

1.38

15

11

DPPB

(BHT)2AlMe

MMA

400:4:1

TOL

20

100

255

1.36

16

12

DPPH

(BHT)2AlMe

MMA

400:4:1

TOL

15

100

254

1.35

16

13e

μHex[P(NIiPr)Ph]2

(BHT)2AlMe

MMBL

400:4:1

DCM

2

100

(73.6)

1.28

78

14e

μHex[P(NIiPr)Ph]2

(BHT)2AlMe

MMBL

800:4:1

DCM

10

100

(115)

1.17

91

15e

μHex[P(NIiPr)Ph]2

(BHT)2AlMe

MMBL

1600:4:1

DCM

120

100

(200)

1.07

96

16e

μHex[P(NIiPr)Ph]2

(BHT)2AlMe

MMBL

3200:4:1

DCM

720

100

(435)

1.31

108

  1. TOL toluene, DCM dichloromethane.
  2. aConditions: carried out at RT; [M]0 = 0.936 mol/L.
  3. bMonomer conversions measured by 1H NMR.
  4. cMn and Ð (Mw/Mn) determined by GPC relative to PMMA standards in DMF.
  5. dInitiator efficiency (I*)% = Mn(calcd)/Mn(exptl) × 100, where Mn(calcd) = [MW(MMA)]([MMA]0/[I]0) (conversion) + MW of chain-end groups.
  6. eAbsolute molecular weight (Mw) measured by GPC coupled with a light scattering detector.
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