ISSN:
0268-2605
Keywords:
precursor
;
ceramic
;
thermolysis
;
silicon
;
carbodi-imide
;
boron
;
hydroboration
;
plastic forming
;
Chemistry
;
Industrial Chemistry and Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The synthesis, by two different reaction pathways, of boron-modified polysilylcarbodi-imides of general type {B[C2H4Si(R)NCN]3}n (R =singly bonded organic ligand) and the plastic-forming and the thermal behavior of these polymers are described. Compounds {B[C2H4Si(R)NCN]3}n [2a, R = H; 2b, R = CH3; 2c, R = (NCN)0.5] can be obtained by treatment of the vinyl-substituted polysilylcarbodi-imides [(H2C=CH)(R)SiNCN]n [1a, R = H; 1b, R = CH3; 1c, R = (NCN)0.5] with borane dimethylsulfide BH3·S(CH3)2. The polysilylcarbodi-imides 1a-1c themselves are accessible via the reaction of vinyl-substituted chlorosilanes (H2C=CH)-(R)SiCl2 with cyanamide H2N-C≡N in the presence of pyridine or by a non-oxide sol-gel process of vinylated chlorosilanes and bis(trimethylsilyl)carbodi-imide, (H3C)3SiN=C=NSi(CH3)3. In the second method for the synthesis of 2a-2c, hydroboration of vinyl-substituted chlorosilanes (H2C=CH)(R)SiCl2 with borane dimethylsulfide, borane trimethylamide or borane triethylamide to yield the tris[(chlorosilyl)ethyl]boranes B[C2H4Si(R)Cl2]3 (3a, R = H; 3b, R = CH3; 3c, R = Cl) is followed by treatment of the as-obtained compounds with bis(trimethylsilyl)carbodi-imide, which results in the formation of the hydroborated polysilylcarbodi-imides 2a-2c. The thermogravimetric behavior of the polymers 1a-1c and 2a-2c up to 2300°C is reported. It is shown that boron-modified polysilylcarbodi-imides are suitable precursors for the preparation of dense bulk ceramics. Therefore, the preparation of green bodies of the hydroborated polysilylcarbodi-imides 2a-2c by plastic forming (PF) is described. A series of experiments points to the fact that the microstructure of the as-obtained ceramic monoliths obtained by subsequent thermolysis of the plastic-formed green bodies is strongly influenced by the conditions during plastic forming. © 1998 John Wiley & Sons, Ltd.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
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