Ethylene-Propylene-Diene Rubber and its Functionalization ...Electronic Supplementary InformationNew...

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

Exo Up Universal V4.7A TA Instruments

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


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


Fig. S10 DSC curve of the ethylene-isoprene copolymer prepared by the complex 1/[Ph3C][B(C6F5)4] (Ip content


-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)


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




130.61°C

120.44°C31.48J/g

-4

-2

0

2

Heat

Flo

w (W

/g)

-100 -50 0 50 100 150Temperature (°C)


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



= 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)


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




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).


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)


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


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




-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)


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




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)


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




-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)


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




-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)


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




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. 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




-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)


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




-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




-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)


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




-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)


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




-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




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)


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


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)


DSC File: Hydroxylation Cp'-THF 1-19-4 0.4MPa ...Operator: lijianfengRun Date: 11-Apr-2017 19:10Instrument: DSC Q2000 V24.11 Build 124


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.

Date post:	01-Jan-2020
Category:	Documents
Upload:	others
View:	9 times
Download:	0 times

Ethylene-Propylene-Diene Rubber and its Functionalization ...Electronic Supplementary InformationNew...

Documents