JPS5912915A - Preparation of octacyclic phenol-formaldehyde resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having improved selective adsorptivity for heavy metallic ions selectively in high yield, by reacting a specific phenol-formaldehyde resin with a hydroxide of Li or Na in a nonaqueous solvent under heating. CONSTITUTION:A phenol-formaldehyde resin, having 700-300 molecular weight and combined form of the reacted formaldehyde of 5-25mol% methylol groups, 7-23mol% dimethylene ether groups and 52-88mol% methylene groups, and obtained by reacting a p-alkylphenol, preferably 1-10C alkyl, e.g. p-tert-butylphenol, with a formaldehyde is reacted with a hydroxide of Li or Na in an amount of 0.1-1.0mol based on the alkylphenol in a nonaqueous solvent, e.g. xylene, in an amount of 5-30 times of that of the resin under heating at 100- 150 deg.C to give the aimed resin of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention pertains to a method for producing a cyclic 7g, nor-formaldehyde resin, and a Vt peak tJ8 lump 2
□ Concerning a method VC for producing fat selectively and at reasonable yields.

Conventionally, activated carbon, diatomaceous earth, various ion conversion resins, and double fats with chelating ability have been used as adsorbents for metal ions such as copper, mercury, and nickel contained in each apple wastewater. Examples include etherified substances, but among these, activated carbon, diatomaceous earth, and ion conversion resins have poor selectivity for negative metal ions, and crown etherified substances have some selectivity. (1) has poor heat resistance, is expensive, and lacks general versatility. It has been discovered that the material exhibits extremely superior selective stratification ability. However, traditional synthetic methods (
-Throwing method), you can selectively use one of the 11 types of ring-shaped throws or even mix each wing into one! ``obtained with high yieldσ
This was not possible due to the above situation in the present invention (rjl!i) This was completed as a result of intensive study beforehand. In other words, the average molecule i1 produced by uninventively reacting p-alkylphenols with formaldehyde (Mn) or 7
00-300 (llt', reacted formaldehyde υ
5 to 25 mol% of bonded form or methylol group, 7 to 23 mol% of dimetele dieter group, 52 to 88 mol% of methylene group
The present invention relates to a method for producing an octocyclic phenol-formaldehyde resin, which involves adding a non-aqueous solvent and a hydroxide of Li or ONa to a mol% phenol-formaldehyde resin and causing a heating reaction.

If the average molecular weight of the phenol-formaldehyde resin used in the present invention is outside the above range, the cyclization reaction may not occur at all.

7.Formaldehyde in resin (1) Regarding the form of the base, methylol group (-C8 heavy 0H) 5-25 mol% dimethylene ether group (-CH*OCH-) 7-25 mol ☆ Methylene: 5 (- CI (theory-) 52-88
If a linear phenol-formaldehyde resin with a structure other than the above is used, the cyclization reaction will not occur.

Next, regarding the raw material alkylphenols for linear phenol/formaldehyde resin, an alkyl group is placed at the rJp-position.
a, since it is used as a dusty chemical 11, avoid the alkyl group (L) type r (for example, methyl cocoon, ethyl group, butyl group (normal butyl group, secondary butyl group, tertiary butyl group) , a pentyl group, a hegetyl group, an octyl group, etc., preferably from 11 to 100.

The present invention V (used in fine phenol-formaldehyde for use in the preparation of formaldehyde vJ,! [mb rtx kanarise L stand synthesis etc. 11:
I/(11 There is no stipulation regarding 0.

Preferably 1 mole of alkylphenol to 1.2
~5.0 moles of formaldehyde 10.05 ~
Add 0.4 mol of an alkali catalyst and react at 60 to 110°C for 2 to 60 hours.

It is preferable to wash the ZPJ-like 7z nor-formaldehyde side fat with a dilute tJi acid aqueous solution or the like in advance and distill off the bath agent and the like under reduced pressure.

In addition to linear phenol formaldehyde, as well as non-aqueous solvents (benzene, toluene, xylene,
Preferably, hegetane, dioxane, etc. are used.
~60'h OL1 or trX 'N aυ Hydroxide a Alkyl 2 Eno If the amount exceeds 64 moles, a chlorination reaction will occur. 0.5 to 2 of the amount of non-aqueous solvent used for small (undesirable) addition of water
．． 0% is preferred.

The reaction temperature is preferably 00 to 150°C, and more preferably 50 to 140°C.

In addition, the reaction time t is 15 to 50 hours or more.
! 5. The method of the present invention (two-stage method) a. Eight-ring phenol formaldehyde resin can be obtained selectively compared to the conventional one-stage method.

The non-invention will be explained below based on reference examples and examples. %
) y xy v:, y 200ml rc#Wt# potassium hydroxide A4.4B (0.08 mol) t-water 2all
Dissolved, added -C and reacted at 511m4j at reflux. After adding diluted J4#1 and washing repeatedly with hydrochloric acid and water, the obtained solid was subjected to a vacuum trajectory to remove methanol-insoluble matter, and methanol-insoluble matter was removed using a chloroform-methanol mixed solvent. Fractional recrystallization was carried out and six yuzu oligomers (hereinafter (
1) (n) (III)) Isolated grapes
(Raw H, QmkGPC, mass spectrum.

'HNMR11R spectrum kI/'L-C' was analyzed.

Figure 1 1J Linear 2-nol-formaldehyde 11 fat v
7-kf chilled product, (1) (n) (l[I) C/J
'HNMR spectrum, g2aos-like 2-enol formaldehyde resin, (1), (II), (Ill
) is the IR spectrum of

'1st-order mono-collapsed 3-ume oligomer i, Ltn■ determined 7C
.

1; GPC elution volume ff 124.2ml Molecular violet 1650n with acetylated product υVPO; GPC
Elution Tanigura 25.7 m1 M/Z 972 III: GPC Yukide Tanidou 27.6 m1 M/2 678 Ill (-OHυ absorption is linear oligomer TO54
00Cl” compared to rsatarc (1) (II)
(Ill) /D 32 D 0cnrl shows that the water is running out.

”Also mVc-D I RTTJ 1100cnrlE
, in NMR, there is an ether bond υ absorption near D4.6pyA. 1
Asked in group T; and -Iflt).

[m] Example 1 60 g (0.4 mol) of p-tert-phytylenol and 64.9 g (0.8 mol) of 67% formalin
Potassium hydroxide4. ．． 48 g (0.08 mol) was distributed and reacted at 100° C. for 5 hours. After the reaction, the cloth was washed with hydrochloric acid and water and dried under reduced pressure to obtain an average molecular weight Mn=1810, 10% methylol groups, 12% dimethylene ether groups, 7% methylene groups.
An 8% linear 2-enol formaldehyde side resin was obtained.

Then, this linear 2 enol formaldehyde resin 1
Add 100ml 1% of xylene to 51, and further add 0.48g (0.02 mol) of lithium hydroxide to 1-Ill (tJ), which was dissolved in water and reacted at 140℃ for 5 hours. □.

The methanol-free product was fractionally recrystallized using a chloroform-methanol mixture and fCo was obtained (1) (
Oligomer tG P C
,') (NMR% As a result of measuring IR spectrum and mass spectrum, reference?Ill (L) Analysis value and complete V(
-Crest tiles.

Example 2 45 g (0.4 mol) of p-methyl 21nol and 57
% formalin 64.9 g (0.8 mol) and potassium hydroxide 4.48 g (0.08 mol) were distributed at 95 °C.
When IMj reaction is 100 reaction wave, light minute yt in Kihana and water
The resin was washed and subjected to vacuum transfer to obtain a υ-shaped phenol formaldehyde resin with an average molecular weight of 31 Mn=880, 11% of methylol, 16% of dimethylene ether groups, and 75% of metele/groups. Tsudeko υ linear phenol/formaldehyde tsukudashi 1
1 g VC xylene ILlOmlt-added plus 2.8 g (0.07 mol) of sodium hydroxide. t1mlυ
Dissolve water vt and add c1ss'C to 8#1? After the reaction occurred, the reaction mixture was extracted with methanol,
Methanol-insoluble '111711 was fractionally recrystallized using a mixed solvent of chloroform and methanol. -+:QJ
A chemical compound equivalent to Kasutan CIJ (/-) 0 isolated oligomer tG P C,'i (NMR, I R
The spectrum and mass spectrum were measured and the 8m mass spectrum of the molecule, m1ao4. Gpcm output volume is 26.5 ml, and in IRE - (JHUJ
It was confirmed that there was VC sint at around 6200 cur' of absorption and that it was connected to water system.

[DAHNMRrl'J 10111111'MiJK
-(J Hrc) The sharp single peak attributed to the t'L ring is clearly visible7j.'E'It:
, R4ng -fi, -CHm -CH3ca absorption was confirmed as a single peak of R7, 0, 4, 0, 2, 6 f'L. Therefore, 1, the obtained l' compound it
7t (1) Formula -t: Referential Examples and Examples Jet J? The yield of Tani oligomer is shown.

Table 1 The VL↓vSiM-like phenol formaldehyde oligomer of the present invention became selectively Flti'T'.

[Brief explanation of the drawing]

Factor 1 a Rock-shaped phenol 9 formaldehyde resin v7 SEf)
it) (L) NMR spectrum, second sigma linear phenol formaldehyde 4! j Monthly, (1), (river)
, (ill) is the IR spectrum of 0

Claims (1)

[Claims] 1. Average molecular weight of 700 to 500 obtained by reacting p-furkylphfunols and formaldehydes
0, reacted formaldehyde υM @ form or methylol group 5-251 mol%, dimethylene ether group 7-251 mol%
25 mol%, methylene group 52-88 mol%, non-aqueous swamp to schenol formaldehyde resin.
AII-form phenol formaldehyde resin (tJ production method 0