JPS6148811B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cyclic phenol-formaldehyde compound, and more specifically, 6
The present invention relates to a method for selectively producing a cyclic phenol formaldehyde compound in high yield. Conventional adsorbents for heavy metal ions such as copper, mercury, and nickel contained in various wastewaters include activated carbon, diatomaceous earth, various ion exchange resins, and resins having chelating ability, such as crown ether compounds. However, among these, activated carbon, diatomaceous earth, and ion exchange resins have poor selectivity for heavy metal ions, and crown ether compounds have some selectivity but are poor in heat resistance, expensive, and lack versatility. The present inventors have discovered that a cyclic phenol-formaldehyde compound made from phenols into which specific substituents have been introduced has an extremely excellent selective adsorption ability for heavy metal ions. However, with the conventional synthesis method (one-step method), it has not been possible to selectively synthesize one of the various cyclic bodies or to obtain various mixtures in high yield. The present invention was completed as a result of intensive studies based on the above circumstances. That is, the present invention is based on the structural formula This invention relates to a method for producing a hexacyclic phenol-formaldehyde compound, which comprises adding a non-aqueous solvent and a hydroxide of K or Rb to a phenol-formaldehyde resin obtained by reacting a phenol with a formaldehyde, and subjecting the mixture to a heating reaction. It is something. When producing the phenol-formaldehyde resin used in the present invention, the type and amount of formaldehyde, the type and amount of catalyst for synthesis, the solvent for synthesis,
Alternatively, various conditions such as synthesis temperature and synthesis time are not specified at all, but preferably 1.2 to 3.0 mol of formaldehyde is added to 1 mol of phenols, and 0.05 to 0.4 mol of an alkali catalyst is added. React at 60-110°C. Note that it is preferable to wash the phenol formaldehyde resin with a dilute aqueous hydrochloric acid solution or the like in advance and distill off the solvent and the like under reduced pressure. Furthermore, the phenol formaldehyde resin used in the present invention has an average molecular weight (n) of 700 to 3000.
The bonding form of the reacted formaldehyde is preferably 5 to 25 mol% of methylol groups, 7 to 23 mol% of dimethylene ether groups, and 52 to 88 mol% of methylene groups. When the average molecular weight is outside the above range, the cyclization reaction is difficult to occur. Regarding the bonding form of formaldehyde in the resin, methylol group (-CH ₂ OH) 5 to 25 mol% dimethylene ether group (-CH ₂ OCH ₂ -)
It is preferably 7 to 23 mol% methylene group ( _-CH2- ) 52 to 88 mol%, and when a phenol formaldehyde resin having a structure other than the above is used, the cyclization reaction is unlikely to occur. Regarding the raw material phenols for phenol formaldehyde resin, compounds in which phenyl or alkyl phenyl groups are substituted at the p-position are used, and the types of alkyl groups include methyl groups, ethyl groups, butyl groups (n-butyl groups), etc. , secondary butyl group, tertiary butyl group),
Preferably, those having 0 to 10 carbon atoms are used, such as pentyl group, heptyl group, and octyl group. As the non-aqueous solvent added to the phenol-formaldehyde resin, benzene, toluene, xylene, heptane, dioxane, etc. are used, and the amount used is preferably 5 to 30 times the weight of the phenol-formaldehyde resin. The K or Rb hydroxide is preferably used in an amount equivalent to 0.1 to 1.0 mole per mole of phenols. If it exceeds 1.0 mol, the cyclization reaction is difficult to occur, and if it is less than 0.1 mol, the reaction rate is undesirably low. The amount of water added is preferably 0.5 to 2.0% by weight of the amount of non-aqueous solvent used. The reaction temperature can be 100 to 150°C, more preferably 130 to 140°C. Incidentally, the reaction time is preferably 3 to 30 hours. The method of the present invention (two-stage method) as described above can selectively obtain a hexacyclic phenol formaldehyde compound compared to the conventional one-stage method. The present invention will be explained below based on Reference Examples and Examples. Reference example (one-step method) 68.4 g (0.4 mol) of p-phenylphenol and 30 g (0.8 mol) of paraformaldehyde were suspended in 200 ml of xylene, 4.48 (0.08 mol) of potassium hydroxide was dissolved in 2 ml of water, and the mixture was heated to reflux temperature. The reaction was carried out for 5 hours. After the reaction, dilute hydrochloric acid was added, the mixture was washed repeatedly with hydrochloric acid and water, and dried under reduced pressure. The obtained solid was extracted with methanol, and the methanol-insoluble matter was fractionally recrystallized using a chloroform-methanol mixed solvent to isolate three types of oligomers (hereinafter referred to as [] [] []). Furthermore, the product was analyzed by GPC, mass spectrometry, 'H NMR, and IR spectroscopy. The analysis results of these compounds were as follows. 1. Melting points were all over 300℃. 2 GPC and molecular weight: GPC elution volume 24.2ml Molecular weight M/Z1456: 〃 25.5ml 〃 1092: 〃 27.3ml 〃 758 3 Infrared absorption spectrum (KBr tablet method) In IR, the absorption of -OH is due to the raw material phenol.
Compared to 3400 cm ^-1 for formaldehyde resin, it is observed at 3200 cm ^-1 for , indicating hydrogen bonding. This is a characteristic of toroids. 4 Nuclear magnetic resonance spectrum (tetrachloride return solvent,
TMS standard) (,,) Both have a sharp single peak around 10.0ppm…―OH
Absorption (Characteristics of cyclic bodies) Relatively sharp multiple peaks at 7.4 to 7.2 ppm...
Ring-H absorption 3.9ppm with a slightly broad single peak...-CH ₂
- (Characteristics of cyclic bodies) Combining the above data, it can be seen that [] [] [] has the following structure. Example 1 68.4 g (0.4 mol) of p-phenylphenol and
64.9 g (0.8 mol) of 37% formalin and 4.48 g (0.08 mol) of potassium hydroxide were mixed and reacted at 100°C for 5 hours. After the reaction, wash thoroughly with dilute hydrochloric acid and water and dry under reduced pressure to obtain an average molecular weight n = 199.0, methylol group.
11%, dimethylene ether 11%, methylene group 78%
A linear phenol-formaldehyde resin was obtained. Next, 100 ml of xylene was added to 17 g of this linear phenol-formaldehyde resin, and 2.1 g (0.02 mol) of rubidium hydroxide dissolved in 1 ml of water was added and reacted at 140° C. for 5 hours. The obtained reaction product was extracted with methanol, and the methanol-insoluble material was fractionally recrystallized using a chloroform-methanol mixed solvent. As a result, only [] was isolated.
The isolated oligomer was subjected to GPC, 'H NMR, IR spectrum, and mass spectrum measurements, and the results were completely consistent with the analytical values of the reference example. Example 2 4-hydroxy, 4'-butylbiphenyl 90.4g
(0.4 mol) 37% formalin 64.9 g (0.8 mol) and potassium hydroxide 4.48 g (0.08 mol) were mixed and reacted at 90°C for 5 hours, thoroughly washed with dilute hydrochloric acid and water, dried under reduced pressure, and average molecular weight n =1330 methylol group 12
%, dimethylene ether group 18%, methylene group 70%
A linear phenol-formaldehyde resin was obtained. Next, 100 ml of xylene was added to 4.5 g of this linear phenol-formaldehyde resin, and 0.6 g (0.01 mol) of potassium hydroxide dissolved in 1 ml of water was added, followed by reaction at 135° C. for 8 hours. The obtained reaction product was extracted with methanol, and the methanol-insoluble material was fractionally recrystallized using a chloroform-methanol mixed solvent. As a result, only the corresponding hexacyclic compound was isolated. The isolated oligomer
GPC, 'H NMR, IR spectrum, and mass spectrum were measured. As a result, the molecular weight according to mass spectrometry was 1344, the GPC elution capacity was 25.5, and the -OH absorption in IR was shifted to around 3200 cm ^-1 , confirming that there was a hydrogen bond. Therefore, it can be seen that the obtained compound is a heptacyclic compound corresponding to the formula [ ] shown in the reference example. Table 1 shows the yield of each oligomer in Reference Examples and Examples.

[Table] According to the present invention, it has become possible to selectively synthesize a hexacyclic phenol formaldehyde compound.

Claims (1)

[Claims] 1. Structural formula Production of a hexacyclic phenol-formaldehyde compound, which is characterized by adding a non-aqueous solvent and a hydroxide of K or Rb to a phenol-formaldehyde resin obtained by reacting a phenol represented by the formula with formaldehyde and subjecting the mixture to a heating reaction. Law. 2. The method for producing a hexacyclic phenol-formaldehyde compound according to claim 1, wherein the phenol is p-phenylphenol. 3 The phenol formaldehyde resin has an average molecular weight of 700 to 3000 and the bonding form of formaldehyde is 5 to 25 mol% of methylol groups, 7 to 23 mol% of dimethylene ether groups, and 52 to 52 mol% of methylene groups.
88 mol% of the hexacyclic phenol formaldehyde compound according to claim 1 or 2.