Preparation of Soluble Polycarbosilane Polymers Using Group 4 Metallocene Catalysts

• Published in: Organometallics Vol. 15; no. 13; pp. 2866 - 2870
• Main Authors: Shaltout, Raef M, Corey, Joyce Y
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 25.06.1996; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; DEHYDROPOLYMERIZATION; ZIRCONOCENE; DEHYDROGENATIVE POLYMERIZATION; SILANES; POLYSILANES
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om960200c

The preparation of a series of carbosilane monomers of the form H3Si−R−SiH3 (primary carbosilane) and H2PhSi−R‘−SiPhH2 (secondary carbosilane) (R = −CH2CH2−, -−CH2CH2SiPh2CH2CH2−, −CH2CH2CH2SiPh2CH2CH2CH2−; R‘ = (CH2) n (n = 1−3), −CH2CH2SiMe2CH2CH2−) is reported. Polymerization of the primary carbosilanes resulted in the formation of insoluble polycarbosilanes in less than 1 h. The secondary carbosilanes, however, yielded polymers that were soluble in common solvents (e.g., CHCl3, C6H6, and THF). GPC analyses of the polymers indicated molecular weights as high as 12 000. The molecular weights were highly dependent on the structure of the monomer and the reaction conditions (temperature, solvent, catalyst concentration, and catalyst nature).