JPS6033126B2 - Production method of 8-cyclic phenol formaldehyde resin - 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 resin selectively and in high yield. Activated carbon, diaphragm,
Examples include various ion exchange resins and resins having chelate compounds, such as crown ether compounds. However, among these, activated carbon, renaissance resin, and ion exchange resin have poor selectivity for heavy metal ions, and crownable compounds have some selectivity but are poor in heat resistance, expensive, and lack versatility. The present inventors have discovered that a cyclic phenol/formaldehyde resin made from phenols into which specific substituents have been introduced has an extremely excellent selective adsorption ability for heavy metal ions. However, with conventional synthesis methods (one-step methods), it has not been possible to selectively synthesize one of the various cyclic bodies or to obtain various mixtures in high yields. The present invention was completed as a result of intensive studies based on the above circumstances. That is, in the present invention, the average molecular weight (Mn) obtained by reacting p-alkylphenols with formaldehyde is 7.
00 to 3000, and the bond form of the reacted formaldehyde is 5 to 25 mol% of methylol group, 7 to 23 mol% of dimethylene ether group, and 52 to 88 mol% of methylene group.
The present invention relates to a method for producing an octacyclic phenol-formaldehyde resin, which is characterized by adding a non-aqueous solvent and a hydroxide of Li or Na to the phenol-formaldehyde resin, and subjecting the mixture to a heating reaction. When the average molecular weight of the phenol-formaldehyde resin used in the present invention is outside the above range, the cyclization reaction does not occur at all and the resin remains linear. Regarding the bonding form of formaldehyde in the resin, 5 to 25 mol% of methylol groups (1 CH20H), 7 to 23 mol% of dimethylene ether groups (1 C and OCH2), and 7 to 23 mol% of methylene groups (1 CQ). ~total mol% is required, and if a linear phenol/formaldehyde resin other than the above configuration is used, the cyclization reaction will not occur. Next, regarding the raw material alkylphenols for linear phenol/formaldehyde resin, compounds in which an alkyl group is substituted at the p-position are used, and the types of alkyl groups are methyl, ethyl, butyl (n-butyl, secondary butyl group, tertiary butyl group),
Preferably, those having 1 to 10 carbon atoms are used, such as a bentyl group, a heptyl group, and an octyl group. When producing the linear phenol formaldehyde resin used in the present invention, the type of formaldehyde,
There are no restrictions on various conditions such as amount, type of catalyst for synthesis, amount, solvent for synthesis, synthesis temperature, synthesis time, etc., but preferably 1.2 to 3.0 mol per mol of alkylphenol. of formaldehyde and 0
．． 60-1 by adding 0.5-0.4 mol of alkali catalyst
1000 for 2 to 30 hours. Note that it is preferable that the linear phenol and formaldehyde resins be washed with a dilute aqueous hydrochloric acid solution or the like in advance, and the solvent etc. be distilled off under reduced pressure. As the non-aqueous solvent added to the linear phenol-formaldehyde resin, benzene, toluene/xylene, heptane, dioxane, etc. are used, and the amount used is preferably 5 to 3 times the weight of the linear phenol-formaldehyde resin. The hydroxide of Li or Na is preferably used in an amount equivalent to 0.1 to 1.0 mol per mol of the alkylphenol. If the amount exceeds 1.0 mol, the cyclization reaction will be difficult to occur;
．． If the amount is less than 1 mole, the reaction rate will be 4.5%, which is undesirable. The amount of water added is 0.5 to 2 of the amount of non-aqueous solvent used.
．． % by weight is preferred. The reaction temperature can be 100-150oC, more preferably 130-140q0. In addition, the reaction time is preferably 3 to 3 hours. The method of the present invention (two-stage method) as described above can selectively obtain an octocyclic phenol-formaldehyde resin 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) 60 molar (0.4 mol) of p-te-butyl fluoride and 30 molar (0.8 mol) of paraformaldehyde were suspended in 200 molar of xylene and 4.48 molar (0.4 mol) of potassium hydroxide was suspended. .0
8 mol) was dissolved in two volumes of water and reacted at reflux temperature for 5 hours. After the reaction, add dilute hydrochloric acid and wash repeatedly with hydrochloric acid and water.
Dry 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 [1)].
0] [m]) was isolated. GPC the product
, mass vector, NM town, analyzed by IR spectroscopy. Figure 1 shows the acetylated product of linear phenol-formaldehyde resin, [1], [b], [m]. Figure 2 shows the linear phenol-formaldehyde resin, [1],

This is an IR spectrum of [0] and [m]. In addition, three types of oligomers 1,0, Machi's GPC,'
NMR and IR spectrum molecular weight was measured. 1:G
PC elution capacity 24.2' Acetylated molecular weight by VPO 16300; GPC
Elution volume 25.7 and M/Z 972 m; GPC elution volume 27.6 [M/Z 678 IR -OH absorption is 340 m for linear oligomer
Compared to 0 arc-1, [1] [b] [m] is 32
This is seen in 00 Hada-1, indicating hydrogen bonding. Also, [Town] has 1100 k-1 in IR and 4 in NM eyes. Absorption of ether bonds is seen near &. Further, 1,0 is a cyclic structure containing only methylene bonds. Combining the above data, it can be seen that 1, D, and m have the following structure. Example 1 60 moles (0.4 mol) of p-te91 butylphenol, 64.9 moles (0.8 mol) of 37% formalin, and 4.48 moles (0.08 mol) of potassium hydroxide were mixed to make 100% The reaction was carried out at ℃ for 5 hours. After the reaction, it was washed with dilute hydrochloric acid and water and dried under reduced pressure to obtain an average molecular weight Mn=
1810, a linear phenol formaldehyde resin containing 10% methylol groups, 12% dimethylene ether groups, and 78% methylene groups was obtained. Next, 15 parts of this linear phenol-formaldehyde resin and 100 parts of xylene were added,
Furthermore, 0.48 molar (0.02 mol) of lithium hydroxide was added to 1
The mixture was dissolved in local water 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 [1] was isolated. The isolated oligomer was analyzed by GPC, NMR, IR spectrum,
The mass vector measurement results completely matched the analytical values of Reference Example 0. Example 2 P-methylphenol 43 mol (0.4 mol) and 37% formalin 64.9 mol (0.8 mol) potassium hydroxide 4.
48 (0.08 mol) was blended and reacted at 95q0 for 8 hours. After the reaction, it was thoroughly washed with dilute hydrochloric acid and water and dried under reduced pressure to obtain a green phenol formaldehyde resin with an average molecular weight Mn=880, 11% methylol groups, 16% dimethylene ether groups, and 73% methylene groups. Next, this linear phenol
100 g of xylene was added to 11 g of formaldehyde resin, and 2.8 g (0.07 mol) of sodium hydroxide dissolved in 1 g of water was added, followed by reaction at 13,500 g 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 a compound corresponding to [1] was isolated. The isolated oligomer was subjected to GPC, 'HNMR,
IR spectrum and mass vector were measured. As a result, the molecular weight by mass vector was 1304, the GPC port capacity was 26.5', and the -OH absorption in IR was 32.
00 cm-1, confirming hydrogen bonding. In addition, in the case of 1'-day NM old, a sharp single peak attributed to -OH was observed after 1-day skin, indicating that it was a cyclic body. In addition, the absorption of -CH2 -Cf18 was confirmed as a single peak at 7.4, 4.0, and 2.3, respectively, during the Ring day. Therefore, the obtained compound was shown in Reference Example [1]
It is considered to be a compound in which the tert-butyl group is a methyl group. Table 1 shows the yield of each oligomer in Reference Examples and Examples. Table 1 According to the present invention, it has become possible to selectively synthesize eight-ring phenol formaldehyde oligomers.

[Brief explanation of the drawing]

Figure 1 shows the NMR spectrum of the acetylated product of linear phenol-formaldehyde resin, [1], [U], [m]. Figure 2 shows the linear phenol-formaldehyde resin, [1], [U], [m].
1], [b], and [m]. Figure 1 Figure 2

Claims (1)

[Claims] 1 The average molecular weight obtained by reacting p-alkylphenols with formaldehyde is 700 to 3000,
A non-aqueous solvent and Li or Na are added to a phenolformaldehyde resin in which the bond form of the reacted formaldehyde 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 8-cyclic phenol-formaldehyde resin, which comprises adding a hydroxide and carrying out a heating reaction.