Chem. J. Chinese Universities ›› 2016, Vol. 37 ›› Issue (10): 1849.doi: 10.7503/cjcu20160271
• Physical Chemistry • Previous Articles Next Articles
TANG Yanhui1,*(), WANG Zhidong2
Received:
2016-04-22
Online:
2016-10-10
Published:
2016-09-23
Contact:
TANG Yanhui
E-mail:clyyanhuitang@bift.edu.cn
Supported by:
CLC Number:
TrendMD:
TANG Yanhui, WANG Zhidong. Theoretical Studies on the Regioselectivity and Stereoselectivity of the Olefin Polymerization Catalyzed by Bridged-metallocene Complexes†[J]. Chem. J. Chinese Universities, 2016, 37(10): 1849.
Fig.3 Key parameters of geometrical structures and free energies information of transition states(TSs) of four olefin insertion modes in the chain initiation process of propylene polymerization catalyzed by catalyst ABond lengths are in nm, bond angles and dihedral angles in degree, energies are in kJ/mol, values in parentheses are zero-point energies.
Catalyst | Pathway | Free energy/(kJ·mol-1) | Energy barrier/(kJ·mol-1) | ||
---|---|---|---|---|---|
2 | TS2-3 | 3 | |||
A | (1,2)si | -17.6 | 49.8 | -68.2 | 67.4 |
(1,2)re | -20.1 | 55.7 | -69.9 | 75.8 | |
(2,1)re | -4.6 | 70.3 | -50.6 | 74.9 | |
(2,1)si | -22.2 | 62.4 | -64.9 | 84.6 | |
B | (1,2)si | 8.8 | 74.5 | -70.3 | 74.5 |
(1,2)re | 11.3 | 69.1 | -64.9 | 69.1 | |
(2,1)re | 8.0 | 98.8 | -51.1 | 98.8 | |
(2,1)si | -1.3 | 82.9 | -44.4 | 84.2 | |
C | (1,2)si | 13.4 | 73.7 | -64.5 | 73.7 |
(1,2)re | 8.8 | 75.8 | -74.9 | 75.8 | |
(2,1)re | NA* | NA | NA | NA | |
(2,1)si | -7.1 | 91.3 | -46.5 | 98.4 |
Table 1 Free energy information of the chain initiation process of propylene polymerization catalyzed by catalyst A, B and C
Catalyst | Pathway | Free energy/(kJ·mol-1) | Energy barrier/(kJ·mol-1) | ||
---|---|---|---|---|---|
2 | TS2-3 | 3 | |||
A | (1,2)si | -17.6 | 49.8 | -68.2 | 67.4 |
(1,2)re | -20.1 | 55.7 | -69.9 | 75.8 | |
(2,1)re | -4.6 | 70.3 | -50.6 | 74.9 | |
(2,1)si | -22.2 | 62.4 | -64.9 | 84.6 | |
B | (1,2)si | 8.8 | 74.5 | -70.3 | 74.5 |
(1,2)re | 11.3 | 69.1 | -64.9 | 69.1 | |
(2,1)re | 8.0 | 98.8 | -51.1 | 98.8 | |
(2,1)si | -1.3 | 82.9 | -44.4 | 84.2 | |
C | (1,2)si | 13.4 | 73.7 | -64.5 | 73.7 |
(1,2)re | 8.8 | 75.8 | -74.9 | 75.8 | |
(2,1)re | NA* | NA | NA | NA | |
(2,1)si | -7.1 | 91.3 | -46.5 | 98.4 |
Fig.4 Free energy profiles of the 2nd and 3rd monomer insertion processes of propylene polymerization catalyzed by catalyst BThe values in parentheses are zero-point energies.
Catalyst | Pathway | ΔG2nd propylene/(kJ·mol-1) | ΔG3rd propylene/(kJ·mol-1) |
---|---|---|---|
A | re | 93.8 | 75.3 |
si | 107.6 | 86.2 | |
B | re | 79.1 | 90.0 |
si | 85.4 | 74.9 | |
C | re | 78.3 | 93.3 |
si | 97.9 | 110.9 |
Table 2 Free energy information of the chain propagation process of propylene polymerization catalyzed by catalysts A, B and C
Catalyst | Pathway | ΔG2nd propylene/(kJ·mol-1) | ΔG3rd propylene/(kJ·mol-1) |
---|---|---|---|
A | re | 93.8 | 75.3 |
si | 107.6 | 86.2 | |
B | re | 79.1 | 90.0 |
si | 85.4 | 74.9 | |
C | re | 78.3 | 93.3 |
si | 97.9 | 110.9 |
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