One-step block-copolymerization of ethylene with styrene by C5Me5/ER-ligated samarium(II) complexes (ER = OAr, SAr)

Macromolecules

Volumn 31, Issue 24, 1998, Pages 8650-8652

  Hou, Zhaomin ^a   Tezuka, Hiroaki ^b   Zhang, Yugen ^a   Yamazaki, Hiroshi ^b   Wakatsuki, Yasuo ^a  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

^b CHUO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; COMPLEXATION; COPOLYMERIZATION; DIFFERENTIAL SCANNING CALORIMETRY; GEL PERMEATION CHROMATOGRAPHY; MOLECULAR STRUCTURE; MOLECULAR WEIGHT DISTRIBUTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLICS; POLYETHYLENES; POLYSTYRENES; SAMARIUM COMPOUNDS;

DICHLOROBENZENE;

BLOCK COPOLYMERS;

EID: 0032302983     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma981250r     Document Type: Article

References (48)

1. Block copolymers, which contain two or more long linear homopolymeric segments boned at terminal sites, generally have uniquely different chemical, physical, and mechanical properties compared to their random or alternating copolymeric analogues and particularly show a great emulsifying or compatibilizing effect in the blending of the corresponding homopolymers. For examples, see: (a) Bradford, E. B.; McKeever, L. D. In Progress in Polymer Science; Jenkins, A. D., Ed.; Pergamon Press: Oxford, U.K., 1971; Vol. 3, p 109. (b) Noshay, A.; McGrath, J. Block Copolymers: Overview and Critical Survey; Academic Press: Orlando, FL, 1977. (c) Fayt, R.; Jerome, R.; Tessie, P. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1269. (d) Cohen, R. E.; Cheng, P. L.; Kofinas, P.; Berney, C. V. Macromolecules 1990, 23, 324.
2. Block copolymers, which contain two or more long linear homopolymeric segments boned at terminal sites, generally have uniquely different chemical, physical, and mechanical properties compared to their random or alternating copolymeric analogues and particularly show a great emulsifying or compatibilizing effect in the blending of the corresponding homopolymers. For examples, see: (a) Bradford, E. B.; McKeever, L. D. In Progress in Polymer Science; Jenkins, A. D., Ed.; Pergamon Press: Oxford, U.K., 1971; Vol. 3, p 109. (b) Noshay, A.; McGrath, J. Block Copolymers: Overview and Critical Survey; Academic Press: Orlando, FL, 1977. (c) Fayt, R.; Jerome, R.; Tessie, P. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1269. (d) Cohen, R. E.; Cheng, P. L.; Kofinas, P.; Berney, C. V. Macromolecules 1990, 23, 324.
3. Block copolymers, which contain two or more long linear homopolymeric segments boned at terminal sites, generally have uniquely different chemical, physical, and mechanical properties compared to their random or alternating copolymeric analogues and particularly show a great emulsifying or compatibilizing effect in the blending of the corresponding homopolymers. For examples, see: (a) Bradford, E. B.; McKeever, L. D. In Progress in Polymer Science; Jenkins, A. D., Ed.; Pergamon Press: Oxford, U.K., 1971; Vol. 3, p 109. (b) Noshay, A.; McGrath, J. Block Copolymers: Overview and Critical Survey; Academic Press: Orlando, FL, 1977. (c) Fayt, R.; Jerome, R.; Tessie, P. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1269. (d) Cohen, R. E.; Cheng, P. L.; Kofinas, P.; Berney, C. V. Macromolecules 1990, 23, 324.
4. Block copolymers, which contain two or more long linear homopolymeric segments boned at terminal sites, generally have uniquely different chemical, physical, and mechanical properties compared to their random or alternating copolymeric analogues and particularly show a great emulsifying or compatibilizing effect in the blending of the corresponding homopolymers. For examples, see: (a) Bradford, E. B.; McKeever, L. D. In Progress in Polymer Science; Jenkins, A. D., Ed.; Pergamon Press: Oxford, U.K., 1971; Vol. 3, p 109. (b) Noshay, A.; McGrath, J. Block Copolymers: Overview and Critical Survey; Academic Press: Orlando, FL, 1977. (c) Fayt, R.; Jerome, R.; Tessie, P. J. Polym. Sci., Polym. Phys. Ed. 1981, 19, 1269. (d) Cohen, R. E.; Cheng, P. L.; Kofinas, P.; Berney, C. V. Macromolecules 1990, 23, 324.
5. Foe examples, see: (a) Fetters, L. J. J. Polym. ScL, Part C 1969, 26, 1. (b) Cowie, J. E. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A., Russo, S., Sigwalt, P., Eds.; Pergamon Press: Oxford, U.K., 1989; Vol. 3, p 17. (c) Boffa, L. S.; Novak, B. M. Tetrahedron 1997, 53, 15367. (d) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53. Bull. Chem. Soc. Jpn. 1997, 70, 1745.
6. Foe examples, see: (a) Fetters, L. J. J. Polym. ScL, Part C 1969, 26, 1. (b) Cowie, J. E. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A., Russo, S., Sigwalt, P., Eds.; Pergamon Press: Oxford, U.K., 1989; Vol. 3, p 17. (c) Boffa, L. S.; Novak, B. M. Tetrahedron 1997, 53, 15367. (d) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53. Bull. Chem. Soc. Jpn. 1997, 70, 1745.
7. Foe examples, see: (a) Fetters, L. J. J. Polym. ScL, Part C 1969, 26, 1. (b) Cowie, J. E. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A., Russo, S., Sigwalt, P., Eds.; Pergamon Press: Oxford, U.K., 1989; Vol. 3, p 17. (c) Boffa, L. S.; Novak, B. M. Tetrahedron 1997, 53, 15367. (d) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53. Bull. Chem. Soc. Jpn. 1997, 70, 1745.
8. Foe examples, see: (a) Fetters, L. J. J. Polym. ScL, Part C 1969, 26, 1. (b) Cowie, J. E. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A., Russo, S., Sigwalt, P., Eds.; Pergamon Press: Oxford, U.K., 1989; Vol. 3, p 17. (c) Boffa, L. S.; Novak, B. M. Tetrahedron 1997, 53, 15367. (d) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53. Bull. Chem. Soc. Jpn. 1997, 70, 1745.
9. Foe examples, see: (a) Fetters, L. J. J. Polym. ScL, Part C 1969, 26, 1. (b) Cowie, J. E. In Comprehensive Polymer Science; Eastmond, G. C., Ledwith, A., Russo, S., Sigwalt, P., Eds.; Pergamon Press: Oxford, U.K., 1989; Vol. 3, p 17. (c) Boffa, L. S.; Novak, B. M. Tetrahedron 1997, 53, 15367. (d) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53. Bull. Chem. Soc. Jpn. 1997, 70, 1745.
10. 3c,d (a) Mecerreyes, D.; Moineau, G.; Dubois, P.; Jerome, R.; Hedrick, J. L.; Hawker, C. J.; Malmstrom, E. E.; Trollsas, M. Angew. Chem., Int. Ed. Engl. 1998, 37, 1274. (b) Guo, H.-Q.; Kajiwara, A.; Morishima, Y.; Kamachi, M. Macromolecules 1996, 29, 2354. (c) Kuntz, I. J. Polym. Sci. 1961, 54, 569. (d) Azuma, N.; Sanda, F.; Tanaka, T.; Endo, T. J. Polym. Sci., Polym. Chem. 1997, 35, 1007 and references therein.
11. 3c,d (a) Mecerreyes, D.; Moineau, G.; Dubois, P.; Jerome, R.; Hedrick, J. L.; Hawker, C. J.; Malmstrom, E. E.; Trollsas, M. Angew. Chem., Int. Ed. Engl. 1998, 37, 1274. (b) Guo, H.-Q.; Kajiwara, A.; Morishima, Y.; Kamachi, M. Macromolecules 1996, 29, 2354. (c) Kuntz, I. J. Polym. Sci. 1961, 54, 569. (d) Azuma, N.; Sanda, F.; Tanaka, T.; Endo, T. J. Polym. Sci., Polym. Chem. 1997, 35, 1007 and references therein.
12. 3c,d (a) Mecerreyes, D.; Moineau, G.; Dubois, P.; Jerome, R.; Hedrick, J. L.; Hawker, C. J.; Malmstrom, E. E.; Trollsas, M. Angew. Chem., Int. Ed. Engl. 1998, 37, 1274. (b) Guo, H.-Q.; Kajiwara, A.; Morishima, Y.; Kamachi, M. Macromolecules 1996, 29, 2354. (c) Kuntz, I. J. Polym. Sci. 1961, 54, 569. (d) Azuma, N.; Sanda, F.; Tanaka, T.; Endo, T. J. Polym. Sci., Polym. Chem. 1997, 35, 1007 and references therein.
13. 3c,d (a) Mecerreyes, D.; Moineau, G.; Dubois, P.; Jerome, R.; Hedrick, J. L.; Hawker, C. J.; Malmstrom, E. E.; Trollsas, M. Angew. Chem., Int. Ed. Engl. 1998, 37, 1274. (b) Guo, H.-Q.; Kajiwara, A.; Morishima, Y.; Kamachi, M. Macromolecules 1996, 29, 2354. (c) Kuntz, I. J. Polym. Sci. 1961, 54, 569. (d) Azuma, N.; Sanda, F.; Tanaka, T.; Endo, T. J. Polym. Sci., Polym. Chem. 1997, 35, 1007 and references therein.
14. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
15. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
16. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
17. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
18. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
19. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
20. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
21. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
22. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
23. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
24. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
25. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
26. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
27. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
28. For examples of group 4 metal-catalyzed random or alternating copolymerization of ethylene with styrene, see: (a) Xu, G. Macromolecules 1998, 31, 2395. (b) Xu, G.; Lin, S. Macromolecules 1997, 30, 685. (c) Arai, T.; Ohtsu, T.; Suzuki, S. Macromol. Rapid Commun. 1998, 19, 327. (d) Thomann, Y.; Sernetz, F. G.; Thomann, R.; Kressler, J.; Mülhaupt, R. Macromol. Chem. Phys. 1997, 198, 739. (e) Sernetz, F. G.; Mülhaupt, R.; Fokken, S.; Okuda, J. Macromolecules 1997, 30, 1562. (f) Fokken, S.; Spaniol, T. P.; Okuda, J.; Sernetz, F. G.; Mülhaupt, R. Organometallics 1997,16, 4240. (g) Sernetz, F. G.; Mülhaupt, R.; Waymouth, R. M. Macromol. Chem. Phys. 1996, 197, 1071. (h) Oliva, L.; Mazza, S.; Longo, P. Macromol. Chem. Phys. 1996, 197, 3115. (i) Pellecchia, C.; Pappalarrdo, D.; D'Arco, M.; Zambelli, A. Macromolecules 1996, 29, 1158. (J) Oliva, L, Caporaso, L.; Pellecchia, C.; Zambelli, A. Macromolecules 1995, 28, 4665. (k) Lee, D.; Yoon, K; Lee, E.; Noh, S.; Byun, G.; Lee, C. Macromol. Rapid Commun. 1995, 16, 265. (l) Aaltonen, P.; Seppala, J.; Matilainen, L.; Leskela, M. Macromolecules 1994, 27, 3136. (m) Miyatake, T.; Mizunuma, K.; Kagugo, M. Makromol. Chem., Macromol. Symp. 1993, 66, 203. (n) Kagugo, M.; Miyatake, T.; Mizunuma, K; Stud. Surf. Sci. Catal. 1990, 56, 517. (o) Longo, P.; Grassi, A.; Oliva, L. Makromol. Chem. 1990, 191, 2387.
29. 3 and polystyrene content of 26 mol %. The structure of the copolymer was not described. See: Fu, P.-F.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 10747.
30. In the case of samarocene complexes, the incorporation of styrene into a polymer unit seemed to be difficult. See: (a) Evans, W. J.; DeCoster, D. M.; Greaves, J. Macromolecules 1995, 28, 7929. (b) Evans, W. J.; Ulibarri, T. A.; Ziller, J. W. J. Am. Chem. Soc. 1990, 112, 219.
31. In the case of samarocene complexes, the incorporation of styrene into a polymer unit seemed to be difficult. See: (a) Evans, W. J.; DeCoster, D. M.; Greaves, J. Macromolecules 1995, 28, 7929. (b) Evans, W. J.; Ulibarri, T. A.; Ziller, J. W. J. Am. Chem. Soc. 1990, 112, 219.
32. (a) Inoue, N.; Jinno, M.; Shiomura, T. JP 0687937, 1994; Chem. Abstr. 1994, 121, 109890h.
33. (b) Naganuma, A.; Tazaki, T.; Machida, S. JP 04130114, 1992; Chem. Abstr. 1993, 118, 7536t.
34. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
35. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
36. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
37. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
38. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
39. For examples, see: (a) Kishimoto, Y.; Morita, H. US. Pat. 4673414, 1984; Chem. Abstr. 1984, 101, 211911q. (b) Teramoto, T.; Goshima, K.; Takeuchi, M. Eur. Pat. 339986,1989; Chem. Abstr. 1990, 112, 181159h. (c) Hattori, I.; Oshima, N. JP 02051503, 1990; Chem. Abstr. 1990, 113, 79282b. (d) Hattori, I, Takashima, A.; Imamura, T. JP 02272004,1990; Chem. Abstr. 1991, 114, 144297x. (e) Molova, J.; Svoboda, P.; Reiss, J.; Miroslav, J. H. Czech Patent, CS 268208, 1990; Chem. Abstr. 1991, 114, 172419g. (f) Chamberlain, L. R.; Gibier, C. J. US. Pat. 5039755, 1991; Chem. Abstr. 1991, 115, 208933g.
40. The synthesis and structure of 2 have been described previously. Complexes 1 and 3 were prepared in a similar way. See: Hou, Z.; Zhang, Y.; Yoshimura, T.; Wakatsuki, Y. Organometallics 1997, 16, 2963.
41. 61-OSKSm (3-THF): C, 61.04; H, 8.01. Found: C, 60.83; H, 7.95.
42. 2. For an example, see ref 9.
43. See Supporting Information for details.
44. For NMR characterization of polystyrenes, see: K. Matsuzaki, T.; Uryu, T. Asakura. NMR Spectroscopy and Stereoregularity of Polymers; Japan Scientific Societies Press/S. Karger AG: Tokyo; 1996; pp 137-156.
45. It has been found that the solubility of polyethylene decreases greatly as the molecular weight increases.
46. 4 are also soluble in THF at room temperature and therefore can be removed by the extraction with THF.
47. The selective formation of block ethylene - styrene copolymers in the present systems strongly suggests that the reactivity of the propagation center of the polyethylene unit is critically different from that of the polystyrene unit, one being able to incorporate both ethylene and styrene, while the other being able to incorporate only the identical monomer. The nature of the metals and the ancillary ligands seems to be an important factor in determining the behavior of the propagation centers. In the present cases, we tentatively assume that the propagation center of the polystyrene unit has some extent of anionic character, which could not allow the insertion of ethylene monomer, and thus the copolymerization reaction might probably be initiated by polymerization of ethylene followed by incorporation of styrene. Further studies are under progress to confirm this hypothesis.
48. 5/OAr-supported Sm(III)-ketyl species, see: (a) Hou, Z.; Fujita, A.; Zhang, Y.; Miyano, T.; Yamazaki, H.; Wakatsuki, Y. J. Am. Chem. Soc. 1998, 120, 754.