Patent Application
20080027175
A 50 ml Schlenk tube with stirrer bar is initially charged with 3.4 ml of toluene. 6.6 ml (71 mmol) of vinyl acetate, 0.08 ml (0.36 mmol) of tris(2,2,2-trifluorethyl) phosphite and 62.3 mg (0.18 mmol) of dibenzoyl peroxide are added successively at 60° C. The reaction mixture is subsequently stirred in the closed Schlenk tube at 70° C. for 2 h. 0.45 g (3.56 mmol) of bis(allyloxy)methane are added to the reaction mixture and then stirred at 70° C. for 20 h. All volatile components are removed in an oil-pump vacuum. The polymer is dissolved in acetone, precipitated with heptane and dried under vacuum to obtain a white powder. Yield: 1.78 g (27%). 1H-NMR (500 MHz, CDCl3): δ=5.89 (t), 5.45 (s), 5.23 (d) poly(bis(allyloxy)methane)), 4.83 (s, br, PVAc), 3.3 (s, br, poly(bis(allyloxy)methane)), 2.13, 1.98, 1.82, 1.72 (4×s, br, PVAc) ppm.
A 50 ml Schlenk tube with stirrer bar is initially charged with 3.4 ml of methanol. 6.6 ml (71 mmol) of vinyl acetate, 0.08 ml (0.36 mmol) of tris(2,2,2-trifluorethyl) phosphite and 62.3 mg (0.18 mmol) of dibenzoyl peroxide are added successively at 60° C. The reaction mixture is subsequently stirred in the closed Schlenk tube at 70° C. for 2 h. Then, 0.55 g (3.56 mmol) of bis(N-acryloylamino)methane are added to the reaction mixture and stirred at 70° C. for 20 h. All volatile components are removed in an oil-pump vacuum. The polymer is dissolved in acetone, precipitated with heptane and dried under vacuum to obtain a white powder. Yield: 6.6 g (98%). 1H-NMR (500 MHz, CDCl3): δ=8.74 (s), 6.48, 6.17, 5.71 (3×dd), 4.87 (s, poly(bis(N-acryloylamino)methane)), 4.83 (s, br, PVAc), 2.42 (s, br, poly(bis(N-acryloylamino)methane)), 2.13, 1.98, 1.82, 1.72 (4×s, br, PVAC) 1.53, (s, br, poly(bis(N-acryloylamino)methane)) ppm.
A 50 ml Schlenk tube with stirrer bar is initially charged with 3.4 ml of methanol. 6.6 ml (71 mmol) of vinyl acetate, 0.08 ml (0.36 mmol) of tris(2,2,2-trifluorethyl) phosphite and 62.3 mg (0.18 mmol) of dibenzoyl peroxide are added successively at 60° C. The reaction mixture is subsequently stirred in the closed Schlenk tube at 70° C. for 2 h. Then, 0.64 ml (3.56 mmol) of divinylbenzene are added to the reaction mixture and stirred at 70° C. for 20 h. All volatile components are removed in an oil-pump vacuum. The polymer is dissolved in acetone, precipitated with heptane and dried under vacuum to obtain a white powder. Yield: 2.12 g (31.4%). 1H-NMR (500 MHz, CDCl3): δ=7.34, 7.25. 7.18, 7.16, 7.05 (aromatic H), 6.63, 5.61, 5.18 (vinylic H), 4.83 (PVAc), 2.76 (cross-linked PDVB), 2.13, 1.98, 1.82, 1.72 (4×s, br, PVAc), 1.58 (cross-linked PDVB) ppm. Tg=42° C. Mw=123000 g/mol. Mw/Mn=2.00.
A 50 ml Schlenk tube with stirrer bar is initially charged with 7.5 ml of xylene. 6.6 ml (71 mmol) of vinyl acetate, 0.08 ml (0.36 mmol) of tris(2,2,2-trifluorethyl) phosphite and 62.3 mg (0.18 mmol) of dibenzoyl peroxide are added successively at 60° C. The reaction mixture is subsequently stirred in the closed Schlenk tube at 70° C. for 2 h. Then, 0.64 ml (3.56 mmol) of divinylbenzene are added to the reaction mixture and stirred at 70° C. for 20 h. All volatile components are removed in an oil-pump vacuum. The polymer is dissolved in acetone. Fractionation of the polymer mixture is achieved by means of preparative GPC. The 1st fraction (copolymer) is dried under vacuum to obtain a white powder. Yield: 0.8 g (12%). 1H-NMR (500 MHz, CDCl3): δ=7.34, 7.25. 7.18, 7.16, 7.05 (aromatic H), 6.63, 5.61, 5.18 (vinylic H), 4.83 (PVAc), 2.13, 1.98, 1.82, 1.72 (4×s, br, PVAC) ppm. Tg=43° C. Mw=500,000 g/mol. Mw/Mn=1.64.
In a 1000 ml round-bottom flask, 167 ml of a 1% methanolic sodium hydroxide solution is heated to 50° C. in a water bath. To this, a solution of 50 g of poly(vinyl acetate-bis(allyloxy)methane)/poly(vinyl acetate) (example 1) in 333 ml of methanol is added dropwise over a period of 30 min. On completion of the addition, the mixture is stirred for 30 min. The white precipitate is filtered, washed to neutrality with methanol and dried under vacuum. Yield: 25.0 g (100%). 1H-NMR (500 MHz, [D2]-D2O): δ=5.89 (t), 5.45 (s), 5.23 (d), 3.3 (s, br, poly(bis(allyloxy)methane)), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44-1.33 (4×s, 1×m, PVOH) ppm. DSC: TG=67° C., Tm=180° C.
In a 1000 ml round-bottom flask, 167 ml of a 1% methanolic sodium hydroxide solution is heated to 50° C. in a water bath. To this, a solution of 50 g of poly(vinyl acetate-bis(N-acryloylamino)methane)/poly(vinyl acetate) (example 2) in 333 ml of methanol is added dropwise over a period of 30 min. On completion of the addition, the mixture is stirred for 30 min. The white precipitate is filtered, washed to neutrality with methanol and dried under vacuum. Yield: 25.0 g (100%). 1H-NMR (500 MHz, [D2]-D2O): δ=8.74 (s), 6.48, 6.17, 5.71 (3×dd), 4.87, 2.42, 1.53, (3×s, poly(bis(N-acryloylamino)methane)). 4.65, 4.46, 3.89, 3.84, 3.31, 1.44-1.33 (4×s, 1×m, PVOH) ppm. DSC: TG=55° C., Tm=184° C.
In a 1000 ml round-bottom flask, 167 ml of a 1% methanolic sodium hydroxide solution is heated to 50° C. in a water bath. To this, a solution of 50 g of poly(vinyl acetate-divinylbenzene)/poly(vinyl acetate) (example 3) in 333 ml of methanol is added dropwise over a period of 30 min. On completion of the addition, the mixture is stirred for 30 min. The white precipitate is filtered, washed to neutrality with methanol and dried under vacuum. Yield: 25.0 g (100%). 1H-NMR (500 MHz, [D2]-D2O): δ=): δ=7.34, 7.25. 7.18, 7.16, 7.05 (aromatic H), 6.63, 5.61, 5.18 (vinylic H), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44-1.33 (4×s, 1×m, PVOH), ppm. DSC: TG=79° C., Tm=183° C.
In a 100 ml round-bottom flask, 16.7 ml of a 1% methanolic sodium hydroxide solution is heated to 50° C. in a water bath. To this, a solution of 5.0 g of poly(vinyl acetate-divinylbenzene) (example 4) in 33.3 ml of methanol is added dropwise over a period of 30 min. On completion of the addition, the mixture is stirred for 30 min. The white precipitate is filtered, washed to neutrality with methanol and dried under vacuum. Yield: 2.5 g (100%). 1H-NMR (500 MHz, [D2]-D2O): δ=7.34, 7.25. 7.18, 7.16, 7.05 (aromatic H), 6.63, 5.61, 5.18 (vinylic H), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44-1.33 (4×s, 1×m, PVOH), ppm. DSC: TG=79° C., Tm=181° C.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP04/13767 | 12/3/2004 | WO | 00 | 4/12/2007 |
