Stereospecifie polymerization of 1,3-butadiene with samarocene-based catalysts

Macromolecules

Volumn 32, Issue 26, 1999, Pages 9078-9079

  Kaita, Shojiro ^a  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; CATALYST SELECTIVITY; LANTHANUM COMPOUNDS; ORGANOMETALLICS; POLYMERIZATION; STEREOCHEMISTRY;

LANTHANOCENE; METHYLALUMINOXANE; SAMAROCENE; STEREOSPECIFIC POLYMERIZATION;

POLYBUTADIENES;

EID: 12944301064     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9913358     Document Type: Article

References (27)

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3. Special Postdoctoral Researcher under the Basic Science Program of RIKEN.
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21. The catalytic activity was strongly dependent on the [MMAO]/ [1] ratio. The polymerization did not occur at the ratio of [MMAO]/[1] < 50. When more than 500 equiv of MMAO was used, the catalytic activity decreased compared to that in the case of [MMAOM1] = 200. The use of PMAO (ordinary methylaluminoxane) instead of MMAO gave a polymer with lower 1,4-cis content under the same conditions.
22. The microstructure of the poly(BD) products was measured by JH NMR and 13C NMR spectroscopy (JNM EX-300) in CDC13. 'H NMR: O4.8-5.2 (=CH2 of 1,2-BD unit), 5.2-5.8 (-CH= of 1,4-BD unit and -CH= of 1,2-BD unit). 13C NMR: <5 27.4 (1,4-cis-BD unit), 32.7 (l,4-/rans-BD unit), 127.7-131.8 (1,4-BD unit), 113.8-114.8 and 143.3-144.7 (1,2-BD unit). The weight-average molecular weight (Mw), the number-average molecular weight (Mn), and the molecular weight distribution (Mw/Afn) of the polymers were measured by GPC [Shodex GPC System-11; detector, RI (RI71); column, GPC KF-508L x 2; temperature, 40 °C; eluent, THF; polystyrene standard].
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25. It has been well-known that the reaction of group 4 metallocene chlorides with MAO generates the corresponding metallocene alkyl cations which are similarly active as those formed in the metallocene alkyl/MAO systems. For examples, see: (a) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143. (b) Bochmann, M. J. Chem. Soc., Dalton Trans. 1996, 255. (c) Cornils, B.; Herrmann, W. A. Applied Homogeneous Catalysis with Organometallic Compounds; VCH: Weinheim, 1996. The fact that the (C5Meö)2Sm(Cl)(THF)MMAO system shows no activity for the polymerization of BD might be due to the difficulty of alkylation of (CsMea SmtClXTHF) by MMAO under the present conditions.
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27. It was established that none of l/Al(i-Bu)3, l/[Ph3C][B(C6F5)4], or AKi-BuMPhaCKBtCeFs).!] showed activity under the same conditions.