Electronic Supplementary Information
Terpolymerization of Ethylene, Propylene with Isoprene via THF-
Containing Half-Sandwich Scandium Catalysts: A New Kind of
Ethylene-Propylene-Diene Rubber and its FunctionalizationRui Tan,a,b Zhenghai Shi,a,b Fang Guo,a,b Lv He,a,b Li Hana,b and Yang Li*a,b
a State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian
116024, China.
b Liaoning Key Laboratory of Polymer Science and Engineering, Dalian 116024, China.
* E-mail: [email protected]
Experiment SectionPropylene/isoprene copolymerization (Table S1, Run 6)
In a glovebox, a toluene solution (15 mL) of isoprene (272.4 mg, 4 mmol) was added into a stainless steel autoclave (100ml). The autoclave was sealed, taken outside and connected to a well-purged propylene line. Propylene (0.2 MPa) was introduced into the autoclave quickly and was saturated by stirring for 1 min. A toluene solution (5 mL) of [1,3-(Me2Si)2C9H5]Sc(CH2SiMe3)2(THF) (11.1 mg, 20 μmol) and [Ph3C][B(C6F5)4] (18.5 mg, 20 μmol) was then added through a springer into the autoclave under vigorous stirring. The total pressure in the reactor was controlled at 0.1 MPa. After 5 min, the polymerization was terminated by methanol. The copolymer was collected by adding another 100 mL of methanol, dried at 30 C under vacuum to a constant weight. The propylene (P) and isoprene (Ip) contents of the propylene-isoprene copolymers were calculated according to the following formulas:Ip mol% = (6 I1+3 I2)/(6 I1+3 I2+2 I3)×1003,4-Ip mol%= 2 I1/(2 I1+I2) ×1001,4-Ip mol%=100−3,4-Ip mol%P mol% = 100−Ip mol%Where I1 is the integration of the resonances from 4.90 to 5.20 ppm (one unsaturated protons of the 1,4-isoprene unit), I2 is the integration of the resonances from 4.50 to 4.85 ppm (two unsaturated protons of the 3,4-isoprene unit), I3 is the integration of the resonances from 0.40 to 0.90 ppm (three methyl protons of the propylene unit).
Ethylene/isoprene copolymerization (Table S1, Run 13)
In a glovebox, a toluene solution (15 mL) of isoprene (681.1 mg, 10 mmol) was charged into a stainless steel autoclave (100 mL). The autoclave was sealed, taken outside and connected to a well-purged ethylene line. Ethylene (0.1 MPa) was introduced into the autoclave quickly and was saturated by stirring for 1 min. A toluene solution (5 mL) of [1,3-(Me2Si)2C9H5]Sc(CH2SiMe3)2(THF) (11.1 mg, 20 μmol) and [Ph3C][B(C6F5)4] (18.5 mg, 20 μmol) was then added through a springer into the autoclave under vigorous stirring. The total pressure in the reactor was controlled at 0.1 MPa, the polymerization was terminated after 2 min by methanol. The copolymer was collected by filtered, washed with methanol and dried at 30 C under vacuum to a constant weight. The isoprene and ethylene contents of the ethylene-isoprene copolymers were calculated according to the literature.2
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2017
Table S1 Ethylene, propylene and isoprene polymerization catalyzed by (C5Me4SiMe3)Sc(CH2SiMe3)2(THF) (1) and [1,3-(Me2Si)2C9H5]Sc(CH2SiMe3)2(THF) (2) /[Ph3C][B(C6F5)4].a
Composition c(mol%)Run [Sc]
Pressure
(MPa)P/E
Ip(mmol)
Time(min)
Yield
(g)Activityb
Ip(1,4/3,4) E PMn
d
(×104)Mw
/Mnd
Tg(Tm) e
(C)
1 f 1 0.2 1/0 2 0.59 886 100 1.2 1.98 -92 2 0.2 1/0 2 1.52 2280 100 2.0 1.91 -4
3 g 1 10 60 0.18 9 5/54/41 24.5 1.31 -384 2 20 5 1.35 810 75/0/25 14.5 1.23 -455 1 0.2 1/0 4 5 0.05 30 34(60/40) 66 n.d. n.d. -256 2 0.2 1/0 4 5 0.27 162 23(74/26) 77 2.3 1.65 -157 1 0.2 2/1 2 1.82 2730 58 42 n.d. h n.d. (104)8 f 1 0.2 5/1 2 1.53 2295 50 50 2.8 1.79 -419 2 0.2 2/1 2 2.25 3375 47 53 n.d. n.d. -44
10 2 0.2 5/1 2 2.09 3135 40 60 3.2 1.90 -3011 1 0.1 0/1 5 2 0.54 810 16(45/55) 84 n.d. n.d. (64,132)12 1 0.1 0/1 10 2 0.41 615 26(42/58) 74 12.4 1.23 -5413 2 0.1 0/1 10 2 0.42 630 30(69/31) 70 n.d. n.d. (131)14 2 0.1 0/1 20 2 0.43 645 41(69/31) 59 24.1 2.11 -47
a Reaction condition: [Sc], 20 μmol; [Ph3C][B(C6F5)4], 20 μmol; Toluene, 20 mL, 25 C; Total pressure, 0.2 MPa. b Given in Kg of polymer per (mol Sc h) . c Determined by 1H-NMR and 13C-NMR. d Determined by GPC in THF. e
Determined by DSC. f Reference 1. g Reference 2. h Not determined.
Fig. S1 The Fineman-Ross plot for the copolymerization of ethylene with propylene catalyzed by the complex
1/[Ph3C][B(C6F5)4]. (F = [E]/[P] in solution, f = [E]/[P] in copolymer)
Fig. S2 The Fineman-Ross plot for the copolymerization of ethylene with propylene catalyzed by the complex
2/[Ph3C][B(C6F5)4]. (F = [E]/[P] in solution, f = [E]/[P] in copolymer)
Fig. S3 The Fineman-Ross plot for the copolymerization of propylene with isoprene catalyzed by the complex
1/[Ph3C][B(C6F5)4]. (F = [P]/[Ip] in solution, f = [P]/[Ip]in copolymer)
Fig. S4 The Fineman-Ross plot for the copolymerization of propylene with isoprene catalyzed by the complex
1/[Ph3C][B(C6F5)4]. (F = [P]/[Ip] in solution, f = [P]/[Ip]in copolymer)
Fig. S5 The Fineman-Ross plot for the copolymerization of ethylene with isoprene catalyzed by the complex
2/[Ph3C][B(C6F5)4]. (F = [E]/[Ip] in solution, f = [E]/[Ip] in copolymer)
Fig. S6 13C-NMR spectrum (100 MHz, CDCl3, 25 oC) of the polyisoprene prepared by the complex
2/[Ph3C][B(C6F5)4] (Table S1, Run 4).
Fig. S7 13C-NMR spectrum (100 MHz, CDCl3, 25 oC) of the ethylene-isoprene copolymer prepared by the
complex 2 /[Ph3C][B(C6F5)4] (Ip content = 41 mol%) (Table S1, Run 14).
-24.66°C(I)-33.85°C
-17.54°C
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150 200 250Temperature (°C)
Sample: tr-1Size: 3.2000 mgMethod: Heat/Cool/Heat
DSC File: C:...\DSC\Cp'-THF P-Ip 0.4-2 5min.001Operator: lijianfengRun Date: 20-Mar-2017 10:13Instrument: DSC Q2000 V24.11 Build 124
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Fig. S8 DSC curve of the propylene-isoprene copolymer prepared by the complex 1/[Ph3C][B(C6F5)4] (Ip content
= 34 mol%) (Table S1, Run 5).
-14.78°C(I)-17.24°C
-13.25°C
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: TR-2Size: 8.4000 mgMethod: Heat/Cool/HeatComment: TR
DSC File: C:...\DSC\Cp'-THF P-Ip 0.6-10 60min.001Operator: lijianfengRun Date: 16-Dec-2016 17:53Instrument: DSC Q2000 V24.11 Build 124
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Fig. S9 DSC curve of the propylene-isoprene copolymer prepared by the complex 2/[Ph3C][B(C6F5)4] (Isoprene
content = 23 mol%) (Table S1, Run 6).
64.76°C
30.46°C19.89J/g
132.15°C
123.07°C1.191J/g
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-3Size: 9.9000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\Cp'-THF E-Ip 0.1-5 0.2MPa 2min.001Operator: lijianfengRun Date: 10-Apr-2017 14:18Instrument: DSC Q2000 V24.11 Build 124
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Fig. S10 DSC curve of the ethylene-isoprene copolymer prepared by the complex 1/[Ph3C][B(C6F5)4] (Ip content
= 16 mol%) (Table S1, Run 11).
-53.63°C(I)-57.05°C
-51.91°C
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-4Size: 12.7000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: ...\Cp'-THF E-Ip 0.1-10 0.2MPa 2min.001Operator: lijianfengRun Date: 10-Apr-2017 15:19Instrument: DSC Q2000 V24.11 Build 124
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Fig. S11 DSC curve of the ethylene-isoprene copolymer prepared by the complex 1/[Ph3C][B(C6F5)4] (Ip content
= 26 mol%) (Table S1, Run 12).
130.61°C
120.44°C31.48J/g
-4
-2
0
2
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-2Size: 6.9000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\DSC\Ind-THF E-P 0.1-10 2min.001Operator: lijianfengRun Date: 11-Apr-2017 17:08Instrument: DSC Q2000 V24.11 Build 124
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Fig. S12 DSC curve of the ethylene-isoprene copolymer prepared by the complex 2/[Ph3C][B(C6F5)4] (Ip content
= 30 mol%) (Table 1, Run 13).
-47.28°C(I)-50.34°C
-44.50°C
-2.0
-1.5
-1.0
-0.5
0.0
0.5
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: TR-5Size: 9.3000 mgMethod: Heat/Cool/HeatComment: TR
DSC File: C:...\DSC\Ind-THF E-Ip 0.1-20 5min.001Operator: lijianfengRun Date: 26-Dec-2016 15:29Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S13 DSC curve of the ethylene-isoprene copolymer prepared by the complex 2/[Ph3C][B(C6F5)4] (Ip content
= 41 mol%) (Table S1, Run 14).
Fig. S14 1H-NMR spectra (400 MHz, CDCl3, 25 oC) of the ethylene-propylene-isoprene terpolymer prepared by
the complex 1/[Ph3C][B(C6F5)4] (Table 1, Runs 1, 3 and 4).
Fig. S15 1H-NMR spectra (400 MHz, CDCl3, 25 oC) of the ethylene-propylene-isoprene terpolymer prepared by
the complex 1/[Ph3C][B(C6F5)4] (Table 1, Runs 79).
-53.19°C(I)-55.71°C
-46.44°C
114.07°C
101.31°C7.406J/g
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-3Size: 11.4000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\DSC\Cp'-THF 1-5-1 0.2MPa 2min.001Operator: lijianfengRun Date: 11-Apr-2017 18:09Instrument: DSC Q2000 V24.11 Build 124
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Fig. S16 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 16 mol%, E content = 77 mol%) (Table 1, Run 2).
-45.77°C(I)-48.70°C
-43.76°C
115.64°C
110.63°C1.519J/g
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tanrui-20160919-Tr-1Size: 10.2000 mg DSC File: C:...\DSC\Cp'-THF E-P-Ip 1-5-4.001
Operator: wysRun Date: 19-Sep-2016 19:44Instrument: DSC Q20 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S17 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 13 mol%, E content = 72 mol%) (Table 1, Run 3).
-53.12°C(I)-55.24°C
-51.49°C111.86°C
104.41°C2.296J/g
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: TR-8Size: 6.2000 mgMethod: Heat/Cool/HeatComment: TR
DSC File: C:...\DSC\Cp'-THF E-P-Ip 1-19-2 5min.001Operator: lijianfengRun Date: 27-Dec-2016 10:54Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S18 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 5 mol%, E content = 66 mol%) (Table 1, Run 7).
108.06°C
94.19°C2.113J/g
-52.55°C(I)-56.28°C
-51.36°C
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-1Size: 15.0000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\DSC\Cp'-THF 1-19-1 0.4MPa 2min.001Operator: lijianfengRun Date: 10-Apr-2017 12:17Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S19 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 10 mol%, E content = 64 mol%) (Table 1, Run 8).
-50.61°C(I)-53.12°C
-49.30°C
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150 200Temperature (°C)
Sample: tr-3Size: 5.4000 mgMethod: Heat/Cool/Heat
DSC File: C:...\Cp'-THF E-P-Ip 1-19-4 0.4MPa.002Operator: lijianfengRun Date: 20-Mar-2017 13:24Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S20 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 18 mol%, E content = 62 mol%) (Table 1, Run 9).
-50.82°C(I)-52.86°C
-49.46°C
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150 200 250Temperature (°C)
Sample: tr-5Size: 5.2000 mgMethod: Heat/Cool/Heat
DSC File: C:...\Cp'-THF E-P-Ip 1-19-8 0.4MPa.001Operator: lijianfengRun Date: 20-Mar-2017 15:52Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S21 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Ip content = 26 mol%, E content = 60 mol%) (Table 1, Run 10).
Fig. S22 GPC curves of the ethylene-propylene-isoprene terpolymer prepared by the complex 1/[Ph3C][B(C6F5)4]
(Table 1, Runs 3, 4, 7 and 8).
Fig. S23 1H-NMR spectra (400 MHz, CDCl3, 25 oC) of the ethylene-propylene-isoprene terpolymer prepared by
the complex 2/[Ph3C][B(C6F5)4] (Table 2, Runs 14).
Fig. S24 1H-NMR spectra (400 MHz, CDCl3, 25 oC) of the ethylene-propylene-isoprene terpolymer prepared by
the complex 2/[Ph3C][B(C6F5)4] (Table 2, Runs 68).
Fig. S25 13C-NMR spectrum (100 MHz, C2D2Cl4, 25 oC) of ethylene-ter-propylene-ter-isoprene terpolymers
prepared by the complex 2 /[Ph3C][B(C6F5)4] (Ip content = 9 mol%, E content = 57 mol%) (Table 2, Run 6).
112.45°C
103.84°C21.64J/g
-4
-2
0
2
Heat
Flo
w (W
/g)
-150 -100 -50 0 50 100 150Temperature (°C)
Sample: TR-2Size: 3.6000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\DSC\Ind-THF E-P-Ip 1-5-1 2min.001Operator: lijianfengRun Date: 24-Apr-2017 15:25Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S26 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 5 mol%, E content = 75 mol%) (Table 2, Run 1).
-49.92°C(I)-54.07°C
-45.63°C
110.65°C
99.57°C4.599J/g
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: TR-7Size: 7.0000 mgMethod: Heat/Cool/HeatComment: TR
DSC File: C:...\DSC\Ind-THF E-P-Ip 1-5-2 5min.001Operator: lijianfengRun Date: 27-Dec-2016 09:53Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S27 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 9 mol%, E content = 75 mol%) (Table 2, Run 2).
-50.24°C(I)-53.33°C
-47.91°C
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-150 -100 -50 0 50 100 150Temperature (°C)
Sample: TR-4Size: 8.9000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: C:...\DSC\Cp'-THF E-P-Ip 1-5-8 5min.001Operator: lijianfengRun Date: 24-Apr-2017 17:42Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S28 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 27 mol%, E content = 60 mol%) (Table 2, Run 3).
-52.71°C(I)-54.99°C
-48.73°C
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150 200 250Temperature (°C)
Sample: tr-7Size: 5.4000 mgMethod: Heat/Cool/Heat
DSC File: C:...\DSC\Ind-THF E-P-Ip 1-19-4.001Operator: lijianfengRun Date: 20-Mar-2017 18:20Instrument: DSC Q2000 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S29 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 9 mol%, E content = 57 mol%) (Table 2, Run 6).
-51.55°C(I)-53.97°C
-49.22°C
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: TR-10Size: 4.5000 mgMethod: Heat/Cool/HeatComment: TR
DSC File: C:...\Ind-2MeTHF E-P-Ip 1-19-4 15min.001Operator: lijianfengRun Date: 19-Dec-2016 15:35Instrument: DSC Q2000 V24.11 Build 124
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Fig. S30 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 24 mol%, E content = 49 mol%) (Table 2, Run 7).
-47.48°C(I)-50.18°C
-45.15°C
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tanrui-20161009-tr-4Size: 7.5000 mg DSC File: C:...\DSC\Ind-THF E-P-Ip 1-19-8.001
Operator: wysRun Date: 09-Oct-2016 21:30Instrument: DSC Q20 V24.11 Build 124
Exo Up Universal V4.7A TA Instruments
Fig. S31 DSC curve of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Ip content = 43 mol%, E content = 38 mol%) (Table 2, Run 8).
Fig. S32 GPC curves of the ethylene-propylene-isoprene terpolymer prepared by the complex 2/[Ph3C][B(C6F5)4]
(Table 2, Runs 68).
-48.79°C(I)-50.89°C
-48.10°C
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-7Size: 4.6000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: 1,4-100% Epoxidation Cp'-THF 1-19-4 0...Operator: lijianfengRun Date: 10-Apr-2017 18:20Instrument: DSC Q2000 V24.11 Build 124
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Fig. S33 DSC curve of the epoxidized ethylene-propylene-isoprene terpolymer.
-38.90°C(I)-45.24°C
-35.60°C
-3
-2
-1
0
1
Heat
Flo
w (W
/g)
-100 -50 0 50 100 150Temperature (°C)
Sample: tr-4Size: 1.6000 mgMethod: Heat/Cool/HeatComment: tanrui
DSC File: Hydroxylation Cp'-THF 1-19-4 0.4MPa ...Operator: lijianfengRun Date: 11-Apr-2017 19:10Instrument: DSC Q2000 V24.11 Build 124
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Fig. S34 DSC curve of the hydroxylated-chlorinated ethylene-propylene-isoprene terpolymer.
References
1 R. Tan, F. Guo and Y. Li, Polym. Chem., 2017, 8, 615–623.
2 L. Pan, K. Y. Zhang, M. Nishiura and Z. M. Hou, Angew. Chem. Int. Ed., 2011, 50, 12012–12015.