Method for preparing carborane-siloxane polymer under catalysis of Lewis acid
A Lewis acid, catalytic preparation technology, applied in chemical instruments and methods, compounds of group 4/14 elements of the periodic table, organic chemistry, etc., can solve the problems of difficulty in increasing the degree of polymerization, large steric hindrance, etc., and achieve simple operation Ease of operation, easy control of reaction conditions, and concise process flow
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Embodiment 1
[0032] Embodiment 1: the preparation of two (chloro-dimethylsilyl)-1,7-carborane
[0033] In inert gas N 2 Under protection, 0.72g (5mmol) of 1,2-dicarbo-closed-dodecaborane was dissolved in 30mL of anhydrous diethyl ether, which was clear and transparent. 11 mmol of n-butyllithium was injected into the ether solution of carborane within 5 minutes, and reacted at 0°C for 3 hours under magnetic stirring. The reaction solution was slowly added to 11 mmol of dimethyldichlorosilane at 0° C., and then reacted at room temperature for 12 hours under stirring. The product was filtered to remove lithium chloride, and the filtrate was evaporated to dryness to obtain bis(chloro-dimethylsilyl)-1,2-carborane, which was heated at 350° C. in a quartz tube for 5 hours to obtain a light yellow semi-solid bis( Chloro-dimethylsilyl)-1,7-carborane. 1 H-NMR (CDCl 3 ): δ=0.24ppm (m, 12H, CH 3 ), δ=1.69~2.95ppm (m, 10H, B 10 h 10 ). FTIR: v(3069cm -1 ), C-H; v(2603cm -1 ), B-H; v(1260cm -...
Embodiment 2
[0034] Embodiment 2: the preparation of carborane-siloxane polymer I (shown in formula 1)
[0035]
[0036] Formula 1: Polymer I
[0037] Dissolve 1.66 g (5 mmol) of bis(chloro-dimethylsilyl)-1,7-carborane obtained in Example 1 in 50 mL of tetrahydrofuran, and add 11 mmol of anhydrous methanol dropwise at 65° C., while passing through N 2 Bubble out by-produced HCl. After reacting for 3 hours, bis(methoxy-dimethylsilyl)-1,7-carborane was obtained. Add 3 mg anhydrous FeCl 3 As a catalyst, bis(methoxy-dimethylsilyl)-1,7-carborane was reacted with 11 mmol of dimethyldichlorosilane at 150° C. for 24 hours. Then the low boilers were removed under reduced pressure, and the resulting polycondensation product was washed with acetone until it was washed with NH 4 CNS test until no iron ion, vacuum drying to obtain a rubbery polymer. T g =-35°C, 2.2% weight loss in hot air at 400°C, 15.3% weight loss at 600°C.
Embodiment 3
[0038] Embodiment 3: the preparation of carborane-siloxane polymer II (shown in formula 2)
[0039]
[0040] Formula 2: Polymer II
[0041] in N 2 In an anhydrous and oxygen-free environment under protection, 0.72g (5mmol) of 1,7-dicarbo-closed-dodecaborane was dissolved in 30mL of tetrahydrofuran, and reacted with 11mmol of tert-butyllithium to obtain 1,2-bis Lithium substituted carboranes. It was slowly added into 11 mmol of methylphenyldichlorosilane under stirring in an ice-water bath, and then reacted at room temperature for 20 hours. The reaction product was filtered, and the filtrate was collected. 65℃, through N 2 Under bubbling, 11 mmol of anhydrous methanol was added dropwise to the filtrate and reacted for 5 hours to obtain bis(methoxy-methylphenylsilyl)-1,7-carborane. With 5 mg anhydrous AlCl 3 As a catalyst, bis(methoxy-methylphenylsilyl)-1,7-carborane and equimolar methylphenyldichlorosilane undergo polycondensation, and react at 180°C for 48 hours to ob...
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