Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes
Abstract
:1. Introduction
2. Experimental Section
2.1. Materials
2.2. Synthesis of Titanium Complexes
2.2.1. Synthesis of (Methylphenyl)silylene-Bridged Ligand L1
2.2.2. Synthesis of (Diphenyl)silylene-Bridged Ligand L2
2.2.3. Synthesis of (Methylphenyl)silylene-Bridged Complex 1
2.2.4. Synthesis of (Diphenyl)silylene-Bridged Complex 2
2.3. Polymerization Procedure
2.4. Analytical Procedure
3. Results and Discussion
3.1. Molecular Structure of Complexes
3.2. Propylene Polymerization
3.3. Mechanical Properties of Polymers
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Complex | 1 | 2 |
---|---|---|
CCDC 1539497 | CCDC 1866644 | |
moiety formula | C46H58NsiTi, 0.5(C6H14) | C48H53NSiTi |
sum formula | C46H58NSiTi | C48H53NSiTi |
formula weight | 700.92 | 719.90 |
crystal system | Triclinic | Monoclinic |
space group | P | P1 21/c1 |
a (Å) | 10.3068(10) | 12.3795(12) |
b (Å) | 13.0737(13) | 9.9527(10) |
c (Å) | 15.1704(15) | 32.554(3) |
α (deg) | 98.411(2) | 90 |
β (deg) | 94.191(2) | 91.065(2) |
γ (deg) | 93.938(2) | 90 |
V (Å3) | 2010.3(3) | 4010.3(7) |
Z | 2 | 4 |
F (000) | 754 | 1536 |
density(calcd.) (g·cm−3) | 1158 | 1192 |
absorption coefficient μ (mm−1) | 0.274 | 0.277 |
theta range for data collection | 1.922 to 25.497° | 1.251 to 28.362° |
reflections collected | 14,202 | 33,691 |
independent reflections | 7483 | 9964 |
final R indices [I > 2δ(I)] | [R(int) = 0.0258] | [R(int) = 0.0917] |
R1 = 0.0389 | R1 = 0.0556 | |
wR2 = 0.0965 | wR2 = 0.1060 |
Parameter | F [35] | 1 | 2 |
---|---|---|---|
Ti–C(1) | 2.267(3) | 2.238(17) | 2.245(3) |
Ti–C(2) | 2.413(3) | 2.449(18) | 2.441(3) |
Ti–C(3) | 2.576(3) | 2.638(18) | 2.570(3) |
Ti–C(4) | 2.569(3) | 2.595(17) | 2.525(2) |
Ti–C(5) | 2.394(3) | 2.347(17) | 2.370(2) |
Ti(1)–N(1) | 1.920(2) | 1.934(15) | 1.954(2) |
Ti(1)–Si(1) | 2.848(11) | 2.846(6) | 2.833(9) |
N(1)–Ti(1)–C(1) | 77.74(11) | 77.99(6) | 77.41(9) |
Ti(1)–N(1)–Si(1) | 101.76(12) | 100.89(7) | 100.10(10) |
N(1)–Si(1)–C(1) | 93.88(13) | 93.32(7) | 94.27(11) |
Entry | Catalyst | Pressure (atm) | Time (min) | Yield (g) | Activity (kg mol−1 h−1) | Mnb (×104) | Mw/Mnb | Tmc (°C) | Tgc (°C) |
---|---|---|---|---|---|---|---|---|---|
1 | 1 | 1 | 12 | 0 | 0 | - | - | - | - |
2 | 2 | 1 | 12 | 0 | 0 | - | - | - | - |
3 d | F | 1 | 12 | 0.36 | 91 | 4.38 | 1.27 | - e | −4.3 |
4 | 1 | 4 | 20 | 0.54 | 162 | 25.7 | 2.18 | - e | −4.0 |
5 | 2 | 4 | 20 | 0.18 | 54 | 13.2 | 2.37 | - e | −3.3 |
6 | F | 4 | 20 | 1.20 | 360 | 34.8 | 2.42 | - e | −4.6 |
7 | 1 | 8 | 20 | 1.99 | 597 | 54.8 | 2.14 | - e | −3.7 |
8 | 2 | 8 | 20 | 0.62 | 186 | 49.3 | 2.05 | - e | −4.0 |
9 | F | 8 | 20 | 2.34 | 702 | 60.1 | 1.89 | - e | −3.4 |
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Wang, H.; Li, Y.; Cai, Z. Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes. Polymers 2018, 10, 1075. https://doi.org/10.3390/polym10101075
Wang H, Li Y, Cai Z. Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes. Polymers. 2018; 10(10):1075. https://doi.org/10.3390/polym10101075
Chicago/Turabian StyleWang, Huajin, Yanqing Li, and Zhengguo Cai. 2018. "Substituent Effects of Phenyl Group on Silylene Bridge in Stereospecific Polymerization of Propylene with C1-Symmetric Ansa-Silylene(fluorenyl)(amido) Dimethyl Titanium Complexes" Polymers 10, no. 10: 1075. https://doi.org/10.3390/polym10101075