新規な塗料用樹脂原料の合成と応用-3-2,2,6,6-テトラキス(β-カルボキシエチル)シクロヘキサノン
スポンサーリンク
概要
- 論文の詳細を見る
In the series of the development of new raw materials of resins, 2, 2, 6, 6-tetrakis- (β-carboxyethyl) cyclohexanone (Polydic Acid) :<BR>HOOCCH<SUB>2</SUB>CH<SUB>2</SUB>HOOCCH<DUB><SUB>2</SUB>-C-O=C-C-CH<SUB>2</SUB>CH<SUB>2</SUB>COOH-CH<SUB>2</SUB>CH<SUB>2</SUB>-CH<SUB>2</SUB>-CH<SUB>2</SUB>-CH<SUB>2</SUB><BR>was prepared as a polybasic acid from cyclohexanone and acrylonitrile. In the first step cyclohexanone was cyanoethylated in the presence of a strong base in tertiary butyl alcohol, and in the second step the cyanoethylated cyclohexanone was hydrolysed with caustic soda and water and then acidified with hydrochloric acid. After recrystallized from water the white crystalline product was obtained in 99% purity, the yield of which is about 80% as a whole.<BR>The rate of esterification of Polydic Acid comparing with trimellitic and phthalic acids was measured at 170,190 and 210°C at the equivalent ratio with lauryl alcohol in the catalyst-free fusion system. In general, the rate of esterification in such a system depends on the third order reaction. But in this case the rate depends on the second order reaction and the rate constants of Polydic, trimellitic, and phthalic acids at 190°C are 3. 6, 1. 5, and 1. 2 x 10<SUP>-2</SUP>g.eq./<I>l</I>. min., respectively, and the activation energy of them are 10. 13, 9. 81, and 7. 51 kcal./g.eq., respectively. It is easily seen that Polydic Acid is more reactive than trimellitic and phthalic acids.<BR>The properties of tetra-<I>n</I>-alkyl esters (such as <I>n</I>-butyl, <I>n</I>-hexyl and <I>n</I>-octyl esters) of Polydic Acid were evaluated for plasticizers. While tetra-<I>n</I>-butyl ester is more compatible with many resins and plastics than almost all other plasticizers, tetra-<I>n</I>-octyl ester is the most suitable for the plasticizer of poly (vinyl chloride.) It is rather inferior in the plasticizing effect especially at low temperature, but superior in the migration-and extraction-resistance than tri-<I>n</I>-octyl trimellitate. It can be used as well for the heat-resistant cable varnish as tri-<I>n</I>-octyl trimellitate.<BR>Water-thinnable alkyd resins (linseed modified, oil length 35%) containing 5, 10, 15 and 20% of Polydic Acid were prepared, and they have good stability and water-thinnability. Then water-thinnable black enamel were prepared by blending these alkyd resins with methylated melamine-formaldehyde resin in the ratio of 85 : 15 (weight ratio as non-volatile) and by rolling with carbon black at 5% PWC. Polydic Acid gives considerably soft and flexible films as expected from its structure. When used at high content, Polydic Acid does not give a film of enough water-resistance and many other properties. But, when used moderately (optimum content is about 3-5% in this experiment), it can be used as well for water-thinnable alkyd resins and coatings as trimellitic anhydride. While Polydic Acid and trimellitic anhydride are tetra-and trifunctional, respectively, the amount of the former in alkyd resin corresponds to the equal amount of the latter from the result of a calculation of total average functionality.
- 色材協会の論文
色材協会 | 論文
- 植物由来ポリ乳酸の分解機構および速度
- 東京農工大学 : 工学部有機材料化学科
- 二光子励起用色材の分子設計と応用
- グリコ-ルキトザンの電位差滴定挙動
- ゼ-タポテンシャル法による収着過程に関する研究-7-メタクリル酸メチル-アクリルアミド共重合体/水系における収着過程