JPS6033125B2 - 7-cyclic phenol formaldehyde resin and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 7-cyclic phenol-formaldehyde resin and a method for producing the same.
This article relates to a cyclic phenol/formaldehyde resin and its manufacturing method.

Conventional adsorbents for heavy metal ions such as copper, mercury, and nickel contained in various wastewaters include activated carbon, silica, various ion exchange resins, and resins having chelating ability, such as various 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 have the disadvantages of poor heat resistance, high cost, and lack of versatility. Ta. The present invention provides a novel 7-cyclic phenol-formaldehyde resin that has extremely excellent selective adsorption ability for heavy metal ions, is inexpensive, and has high heat resistance.

That is, the present invention is based on the general formula [wherein R is CnH+1 (n=
(an integer from 1 to 10).

] It supplies heptacyclic phenol formaldehyde resins represented by:

The characteristic of the resin represented by the above general formula is that seven molecules of alkylphenol substituted with a specific alkyl group at the para position form a cyclic body with the hydroxyl group facing inward through seven methylene groups. Hydroxyl groups arranged approximately in a cyclic manner coordinate with heavy metal ions and exhibit selective adhesion. Moreover, this compound has heat resistance and can be produced at low cost. R in the formula is an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, or octyl group.

When R is day or an alkyl group having 11 or more carbon atoms, a cyclic body is not formed and therefore, selective adsorption for heavy metal ions is not exhibited. Next, a general method for preparing the novel compounds of the present invention will be described. First, 1.2 to 3.0 moles of formaldehyde are mixed with 1 mole of p-alkylphenols, and a non-aqueous solvent of 2 to 4 times the weight of the p-alkylphenols is added and suspended. 0.05 of alkali metal hydroxide to p-alkylphenols
~0.5 mol %, preferably 0.5-2.
It is dissolved in 0% water and added, and reacted for 30 to 10 hours at a reaction temperature of 100 to 120°C.

As the P-alkylphenols, alkyl-substituted phenols having 1 to 10 carbon atoms are used, preferably p-methylphenol and p-ten-butylphenol.

As the formaldehyde, paraformaldehyde, which generates formaldehyde during reaction, is used.

Alkali metal hydroxides include Na, K, Rb, and Cs.
, Fr hydroxide, benzene as non-aqueous solvent soot,
Toluene, xylene, heptane, dioxane, etc. are used.

The resulting reaction mixture is made acidic by adding a key acid such as dilute hydrochloric acid, and the solvent is distilled off under reduced pressure to obtain a solid.

The resin of the present invention is purified, for example, as follows. The obtained solid is dissolved in chloroform, methanol is gradually added and separated into each fraction by a fractional recrystallization method.

A fraction with a molecular weight corresponding to a heptacyclic alkylphenol is purified by silica gel adsorption chromatography. That is, chloroform-
The initial eluate was separated using n-hexane (1:1 vol%) as a synerte.

The solvent of this separated liquid is removed under reduced pressure to obtain the resin of the present invention as a powdery solid.

Next, a synthesis example of the heptacyclic phenol formaldehyde resin of the present invention will be shown.

Example 1 60 moles (0.4 moles) of p-ten-butylphenol and 30 moles (0.8 moles) of paraformaldehyde were suspended in 200 moles of dioxane, and 4.5 moles (approximately 0.08 moles) of potassium hydroxide were suspended in 200 moles of dioxane. mol) dissolved in 2 parts of water was added, and the mixture was reacted for 48 hours at a reaction temperature of 110 qo (under reflux).

After about 2 hours, solids began to precipitate. The reaction mixture containing the solid was made acidic by adding dilute hydrochloric acid, and the solvent was distilled off under reduced pressure to obtain a solid. The solid thus obtained is dissolved in chloroform, methanol is gradually added to change the solvent composition, and the solution is separated into five fractions by a fractional recrystallization method.

The outline of each composition was as follows. Fraction 1: 8 cyclics Fraction 2: 8 cyclics + 6 cyclics Fraction 3: 7 cyclics + a small amount of linear oligomer mixture Fraction 4: A small amount of 7 cyclic 10-linear oligomers Fraction 5: Linear oligomers followed by fraction 3 , using silica gel (Wako Gel C300) as an adsorbent and chloroform-n-hexane (
The initial eluate was collected and purified by silica gel adsorption chromatography using 1:1% by volume) as an eluent.

The analysis results of this product were as follows.

1 Melting point>310o0 Not meltable and unmeasurable (characteristic of a cyclic body) 2 Molecular weight Same as 1134*3 Mass vector (7 degrees V) m/el134 (M10) 30%972 (6
(10 nuclear bodies) 8%810 (5 nuclear bodies 10) 3
5% 648 (10 tetranuclear bodies) 100% 4 Nuclear magnetic resonance spectrum (carbon tetrachloride solvent, TMS standard) 6 (leg) 10.3 (sharp single peak -OH)
(Characteristics of cyclic bodies) 7.1 (Sharp single peak Rin
g per day) 3.8 (broad single peak - CH2 -) 1
．． 26 (sharp single peak-C(CH3)3)5
Infrared absorption spectrum (KBr tablet method) wave number (Ka-1)
It was found that the crystal obtained from the results of 3200 (hydrogen bond -OH) (characteristics of a cyclic body) was.

Example 2 43.2 moles (0.4 moles) of P-methylphenol and 37.5 moles (1.0 mole) of paraformaldehyde were suspended in 150 g of dioxane, and 1.6 moles (0.4 moles) of sodium hydroxide were suspended in 150 g of dioxane.
A solution of 0.04 mol) dissolved in 1.5 ml of water was added and reacted at a reaction temperature of 11,000 mol (under reflux) for 36 hours.

Then, dilute hydrochloric acid was added to the reaction mixture containing the solid to make it acidic, and the solvent was distilled off under reduced pressure to obtain a solid. Thereafter, the heptocyclic product was collected and purified by fractional recrystallization and silica gel adsorption chromatography using the method described in Example 1.

The analysis results of this product were as follows. 1 Melting point >
310 Unmeasurable because it does not melt (characteristic of a cyclic body) 2 Molecular weight Same as 840 3 Mass vector (7 ratio V) m/e840 (M10)
720 (6-nuclear body 10) 600 (5-nuclear body 10) 480 (4-nuclear body 10) 4 Nuclear magnetic resonance spectrum (deuterium chloroform solvent, TM
S standard) 6 (chest) 10.3 (sharp single peak, one OH) (ring body characteristics) 7.2 (sharp single peak, Ring day) 3.9 ((sharp single peak , -CH2-)2.2 (sharp single peak, -CH3)
*5 Infrared absorption spectrum (KB Takibishi method) Wavenumber (K-): 3200 (Hydrogen bond, 1OH) (Characteristics of a cyclic body) It was found that the crystal obtained was.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is CnH^2^n^+^1 (n = an integer from 1 to 10). ] Heptacyclic phenol formaldehyde resin. 2 Claim 1 in which R is a tertiary butyl group
7-cyclic phenol/formaldehyde resin described in 1. 3. 1.2 to 3.0 moles of formaldehyde are blended to 1 mole of p-alkylphenols, and a non-aqueous solvent of 2 to 4 times the weight of the p-alkylphenols is added and suspended, Then, 0.05 to 0.5 mol% of an alkali metal hydroxide is added to the p-alkylphenols, and the mixture is reacted at 100 to 120°C for 30 to 100 hours. manufacturing method.