Methacrylic acid

Example 4

In a nitrogen-replaced glove box, 90 g (511 mmol) of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.00 g (10.0 mmol) of BTEE, 1.85 g (5.0 mmol) of DBDT, 0.33 g (2.00 mmol) of AIBN, and 90 g of methoxypropanol were charged into a flask equipped with a stirrer, and then reacted at 60° C. for 23 hours. The polymerization rate was 99.8%, the Mw was 11,800, and the PDI was 1.41.

45 g (317 mmol) of butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 g (290 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.22 g (1.33 mmol) of AIBN, and 70 g of methoxypropanol were added to the obtained solution, and then reacted at 60° C. for 21 hours. The polymerization rate was 99.1%.

After completion of the reaction, the reaction solution was poured into 5 L of heptane, the produced precipitate was suction-filtrated, and then dried, thereby obtaining 155.2 g (yield: 97%) of white powdery block copolymer B. The acid value was 102. The Mw and the PDI were measured after a carboxylic component in the block copolymer was methyl-esterified. The Mw was 17,300 and the PDI was 1.31.

Example 7

In a nitrogen-replaced glove box, 90 g (511 mmol) of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.00 g (6.67 mmol) of BTEE, 1.23 g (3.33 mmol) of DBDT, 0.33 g (1.33 mmol) of AIBN, and 90 g of methoxypropanol were charged into a flask equipped with a stirrer, and then reacted at 60° C. for 24 hours. The polymerization rate was 99.3%, the Mw was 17,200, and the PDI was 1.45.

48 g (338 mmol) of butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 22 g (256 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.22 g (0.67 mmol) of AIBN, and 70 g of methoxypropanol were added to the obtained solution, and then reacted at 60° C. for 24 hours. The polymerization rate was 98.9%.

After completion of the reaction, the reaction solution was poured into 5 L of heptane, the produced precipitate was suction-filtrated, and then dried, thereby obtaining 153.3 g (yield: 96%) of white powdery block copolymer E. The acid value was 90. The Mw and the PDI were measured after a carboxylic component in the block copolymer was methyl-esterified. The Mw was 25,100 and the PDI was 1.29.

Example 3

In a nitrogen-replaced glove box, 90 g (511 mmol) of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.00 g (6.67 mmol) of BTEE, 1.22 g (3.33 mmol) of DBDT, 0.33 g (2.00 mmol) of 2,2′-azobis-isobutyronitrile (trade name: AIBN, manufactured by Otsuka Chemical Co., Ltd., hereinafter referred to as “AIBN”), and 90 g of methoxypropanol were charged into a flask equipped with a stirrer, and then reacted at 60° C. for 16 hours. The polymerization rate was 99.6%, the Mw was 16,200, and the PDI was 1.41.

45 g (317 mmol) of butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 25 g (290 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.22 g (1.33 mmol) of AIBN, and 70 g of methoxypropanol were added to the obtained solution, and then reacted at 60° C. for 22 hours. The polymerization rate was 99.1%.

After completion of the reaction, the reaction solution was poured into 5 L of heptane, the produced precipitate was suction-filtrated, and then dried, thereby obtaining 138.2 g (yield: 86%) of white powdery block copolymer A. The acid value was 104. The Mw and the PDI were measured after a carboxylic component in the block copolymer was methyl-esterified. The Mw was 24,300 and the PDI was 1.49.