Réaction #1772059

Équation de réaction

acrylic acid

methyl hydroquinone

triphenylphosphine

epichlorohydrin

epichlorohydrin

tetrahydrophthalic acid anhydride

propylene glycol monomethyl ether acetate

triphenylphosphine

sodium hydroxide

→

bisphenol A

Solvants

toluene

toluene

Conditions de réaction

Traitement

1. 1
   Températurecooling tube
2. 2
   Autrethermometer, and funnel for continuously dropping
3. 3
   workup.DISSOLUTIONto dissolve it
4. 4
   Températurethe temperature in the reaction container was increased to 150 degrees Celsius
5. 5
   TempératureWith the temperature maintained at 150 degrees Celsius
6. 6
   Autrethe mixture was subjected to reaction for approximately 90 minutes
7. 7
   Autrewas obtained
8. 8
   Autrewas lowered to 40 degrees Celsius
9. 9
   Températurethe mixture was heated to and
10. 10
    Températuremaintained at 45 degrees Celsius
11. 11
    workup.STIRRINGwhile being stirred
12. 12
    workup.WAITthe mixture was further subjected to a 6-hour
13. 13
    Autrereaction
14. 14
    workup.DISTILLATIONwas collected by vacuum distillation
15. 15
    workup.ADDITIONafter which the reaction product containing a by-product salt and toluene
16. 16
    workup.DISSOLUTIONwas dissolved in methyl isobutyl ketone
17. 17
    Lavagewashed with water
18. 18
    AutreAfter an organic solvent layer was separated from water layer, methyl isobutyl ketone
19. 19
    Autrewas removed from the organic solvent layer by vacuum distillation
20. 20
    Autrewas obtained
21. 21
    Températurecooling tube
22. 22
    workup.DISSOLUTIONthe mixture was dissolved
23. 23
    Températureby heat
24. 24
    TempératureThe mixture was heated to 95-105 degrees Celsius
25. 25
    workup.WAITsubjected to a 4-hour
26. 26
    Autrereaction
27. 27
    TempératureThe reaction product was cooled to 80-90 degrees Celsius
28. 28
    workup.WAITthe mixture was subjected to a 5-hour
29. 29
    Autrereaction
30. 30
    AutreAs a result, a solution with a nonvolatile content of 62% was obtained

Mode opératoire

1,5-dihydroxynaphthalene (phenolic hydroxyl group equivalent weight: 80 g/eq.) (224 parts) and bisphenol A-type epoxy resin (EPICOAT 828, manufactured by Japan Epoxy Resin Co., Ltd., epoxy-equivalent weight: 189 g/eq.) (1075 parts) were pre-reacted in a reaction container having a gas-injection tube, stirrer, cooling tube, thermometer, and funnel for continuously dropping an alkaline metal hydroxide solution. The mixture was stirred at 110 degrees Celsius under nitrogen atmosphere to dissolve it. Subsequently, triphenylphosphine (0.65 parts) was added, and the temperature in the reaction container was increased to 150 degrees Celsius. With the temperature maintained at 150 degrees Celsius, the mixture was subjected to reaction for approximately 90 minutes. Thus, an epoxy resin (a) having an epoxy-equivalent weight of 452 g/eq. was obtained. Next, the temperature in the flask was lowered to 40 degrees Celsius, after which epichlorohydrin (1920 parts), toluene (1690 parts) and tetramethylammonium bromide (70 parts) were added, and the mixture was heated to and maintained at 45 degrees Celsius while being stirred. Subsequently, a 48 wt % aqueous solution of sodium hydroxide (364 parts) was continuously dropped into the mixture for 60 minutes, and the mixture was further subjected to a 6-hour reaction. After the reaction was completed, most of the excessive epichlorohydrin and toluene was collected by vacuum distillation, after which the reaction product containing a by-product salt and toluene was dissolved in methyl isobutyl ketone and then washed with water. After an organic solvent layer was separated from water layer, methyl isobutyl ketone was removed from the organic solvent layer by vacuum distillation. Thus, a polynuclear epoxy resin (b) having an epoxy-equivalent weight of 277 g/eq. was obtained. A calculation based on the epoxy-equivalent weight shows that approximately 1.59 alcoholic hydroxide groups out of 1.98 alcoholic hydroxide groups on the epoxy resin (a) was epoxidized in the obtained polynuclear epoxy resin (b). Accordingly, the rate of epoxidation of the alcoholic hydroxide groups was approximately 80%. Next, the polynuclear epoxy resin (b) (277 parts) was put in a flask having a stirrer, cooling tube and thermometer, after which propylene glycol monomethyl ether acetate (290 parts) was added, and the mixture was dissolved by heat. Then, methyl hydroquinone (0.46 parts) and triphenylphosphine (1.38 parts) were added. The mixture was heated to 95-105 degrees Celsius and subjected to a 4-hour reaction, with acrylic acid (72 parts) gradually dropped into it and air continuously blown into it. The reaction product was cooled to 80-90 degrees Celsius, after which tetrahydrophthalic acid anhydride (129 parts) was added, and the mixture was subjected to a 5-hour reaction. As a result, a solution with a nonvolatile content of 62% was obtained. The obtained carboxyl resin had an acid value of 100 mgKOH/g. This solution is hereinafter referred to as “B-4.”

Source