JPS6148812B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cyclic phenol-formaldehyde resin, and more particularly to a method for producing an octocyclic phenol-formaldehyde compound selectively and 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 A method for producing an octocyclic phenol-formaldehyde compound, which comprises adding a non-aqueous solvent and a hydroxide of Li or Na 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 ~110°C for 2-30 hours. 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 etc. under reduced pressure. Furthermore, the phenol formaldehyde resin used in the present invention has an average molecular weight (n) of 700 to 3000.
It is preferable that the bond form of the formaldehyde reacted in is 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 -)
Preferably, the content is 7 to 23 mol %, methylene group (--CH ₂ ) 52 to 88 mol %, and when a phenol formaldehyde resin having a structure other than the above structure is used, the cyclization reaction is unlikely to occur. Regarding the raw material phenols for phenol-formaldehyde resin, compounds in which phenyl or alkylphenyl groups are substituted at the p-position are used,
Furthermore, regarding the type of alkyl group, those having preferably 0 to 10 carbon atoms are selected, such as methyl group, ethyl group, butyl group (normal butyl group, secondary butyl group, tertiary butyl group), pentyl group, heptyl group, octyl group, etc. used. 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 hydroxide of Li or Na is preferably used in an amount equivalent to 0.1 to 1.0 moles 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 0.5 of the amount of non-aqueous solvent used.
~2.0% by weight is preferred. The reaction temperature can be 100 to 150°C, and more preferably 130 to 140°C. In addition, the reaction time is 3
~30 hours is good. The method of the present invention (two-stage method) as described above can selectively obtain an octocyclic 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-stage method) p-phenylphenol 68.4g (0.4 mol)
and 30 g (0.8 mol) of paraformaldehyde are suspended in 200 ml of xylene and 4.48 mol of potassium hydroxide is added.
(0.08 mol) was dissolved in 2 ml of water and reacted at reflux temperature 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 obtain three types of oligomers (hereinafter referred to as []
[ ] [ ]) was isolated. more product
Analyzed by GPC, mass spectrum H NMR, and IR spectrum. The analysis results of these compounds were as follows. 1 Melting point. ．． ．． In both cases, the temperature was 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, -OH absorption is not linear oligomer
Compared to 3400cm ^-1 . ．． So 3200
cm ^-1 , 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
...Slightly broad single peak at 3.9ppm absorption of Ring-H
…—CH ₂ — (Characteristics of a cyclic body) 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, the resin was washed with dilute hydrochloric acid and water and dried under reduced pressure to obtain a linear phenol formaldehyde resin having an average molecular weight n=1990, 11% methylol groups, 11% dimethylene ether groups, and 78% methylene. Next, 100 ml of xylene was added to 17 g of this linear phenol-formaldehyde resin, and 0.48 g (0.02 mol) of lithium hydroxide dissolved in 1 ml of water was added, followed by reaction 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 Reference Example 1. Example 2 4-hydroxy, 3'-ethylbiphenyl 79.2g
(0.4 mol), 64.9 g (0.8 mol) of 37% formalin, and 4.48 g (0.08 mol) of potassium hydroxide at 95°C.
The mixture was allowed to react for 8 hours. After the reaction, it was thoroughly washed with dilute hydrochloric acid and water and dried under reduced pressure to obtain a linear phenol formaldehyde resin with an average molecular weight n=1220, 14% methylol groups, 15% dimethylene ether groups, and 71% methylene groups. Next, add 100 ml of xylene to 20.3 g of this linear phenol formaldehyde resin,
In addition, add 2.8 g (0.07 mol) of sodium hydroxide to 1
The mixture was dissolved in 1 ml of water and reacted 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 heptacyclic compound was isolated. GPC, 'H NMR, IR spectrum, and mass spectrum of the isolated oligomer were measured. As a result, the molecular weight according to mass spectrometry was 1680, and the elution volume of GPC was 24.2 ml, and the -OH absorption was shifted to around 3200 cm ^-1 in IR, which confirmed that there was a hydrogen bond. In addition, in 'H NMR, a sharp single peak attributed to -OH was observed before 10 ppm, indicating that it was a cyclic substance. Also, the absorption of Ring- H is 7.4 ~
7.2ppm as a multiplet, and -C H ₂ -C H ₂
The absorptions of 3.9 and 2. were confirmed as a single peak in formula 3, respectively. Therefore, the obtained compound corresponds to the compound shown in Reference Example [ ] in which the phenyl group is 3-ethylphenyl. 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 an octacyclic phenol formaldehyde compound.

Claims (1)

[Claims] 1. Structural formula An 8-cyclic phenol-formaldehyde compound is produced by adding a non-aqueous solvent and a hydroxide of Li or Na to a phenol-formaldehyde resin obtained by reacting a phenol represented by the formula with formaldehyde and heating the mixture to react. Manufacturing method. 2. The method for producing an octocyclic phenol-formaldehyde compound according to claim 1, wherein the phenol is p-phenylphenol. 3 The bonding form of formaldehyde reacted with phenol formaldehyde resin with an average molecular weight of 700 to 3000 is 5 to 25 mol% of methylol groups, 7 to 23 mol% of dimethylene ether groups, and 52 to 88 mol% of methylene groups. A method for producing an octacyclic phenol formaldehyde compound according to Item 1.