Polysiloxane block copolymers
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example 1
Conversion of Vinyl End-Functional Polysiloxane into Thiol
[0157]20 g vinyl end-functional polydimethylsiloxane (Silmer VIN 100, Siltech) is dissolved in 20 mL toluene. To this is added 550 mg azobisisobutyronitrile and 0.8 mL thioacetic acid. The mixture is sparged with nitrogen for 30 min, then heated at 80° C. for 6 h. It is cooled in ice / water and rinsed with methanol three times. The residual solvent is removed under vacuum.
[0158]15 g of the product is dissolved in 20 mL toluene, and 2 mL 10% methanolic sodium hydroxide is added. The mixture is sparged with nitrogen and stirred for 8 h. It is rinsed with methanol 3 times. The residual solvent is removed under vacuum.
example 2
[0159]To a solution of 25 g vinyl end-functional polydimethylsiloxane (Silmer VIN 200, Siltech) in 20 mL toluene is added 413 mg azobisisobutyronitrile and 0.6 mL thioacetic acid. The mixture is sparged with nitrogen for 30 min, then heated at 80° C. for 7 h. It is allowed to cool and rinsed with methanol three times. The residual solvent is removed under vacuum. To a solution of 2.0 g of this product in 2 ml ether that had been kept on lithium aluminum hydride (LAH) is added 50 mg LAH, and the mixture is stirred at room temperature for 48 h. The mixture is then filtered, and the solvent is removed under vacuum.
example 3
Conversion of Hydroxyl End-Functional Polydimethylsiloxane into Thiol
[0160]20 g hydroxyl end-functional polydimethylsiloxane (Silmer OH100, Siltech) is dissolved in 50 mL dichloromethane. To this is added 2 mL pyridine and 4.0 g p-toluenesulfonyl chloride. The mixture is stirred at room temperature for 24 h. The product is rinsed with methanol 3 times, and the residual solvent is removed under vacuum.
[0161]5 g of the product is dissolved in 15 mL toluene and a solution of 0.45 g potassium thioacetate in 1.5 mL methanol is added. The mixture is sparged with nitrogen for 30 min., then stirred at 105° C. for 24 h. The mixture is allowed to cool, then rinsed with methanol 3 times, and the residual solvent is removed under vacuum. The product is dissolved in 10 mL toluene, and 1 mL 10% methanolic potassium hydroxide is added. The mixture is sparged for 30 min, then refluxed for 1 h. It is cooled in an ice bath, then rinsed with methanol 3 times, and the residual solvent is removed under ...
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