JPS59134788A - Production of dioxane glycol - Google Patents

Abstract

PURPOSE:To produce the titled compound in high yield and purity, with simplified process, without necessitating the recovery of hydroxypivalaldehyde, by reacting trimethylolpropane directly with a liquid produced by aldol reaction or with a liquid obtained by a specific treatment of said aldol reaction product liquid. CONSTITUTION:A liquid containing hydroxypivaldehyde and obtained by the aldol condensation of isobutylaldehyde with HCHO or a liquid obtained by distilling out the unreacted isobutylaldehyde from the above liquid, is subjected to the acetalization reaction with trimethylolpropane in the presence of prefrably an acid catalyst (e.g. HCl, phosphoric acid, methanesulfonic acid, etc.) at 35- 60 deg.C for 3-5hr to obtain dioxane glycol. USE:Synthetic raw material of plasticizer, ink, paint, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing dioxane glycol (hereinafter referred to as DOG) by reacting trimethylolbutane (hereinafter referred to as TMP) and hydroxypivalaldehyde (hereinafter referred to as HPA).

DOG is a polyhydric alcohol with a neo structure and a 1,6-dioxane ring, and can be used as raw materials for organic synthesis, raw materials for synthetic resins, such as plasticizers, lubricating oils, photocurable inks, paints, FRP,
It is useful as a raw material for polyurethane, etc. In particular, since it has two primary alcoholic hydroxyl groups and a dioxane ring, it is expected that when this DOG is further developed into derivatives as a raw material, new compounds with extremely distinctive physical properties will be obtained. Ru.

Until now, there has been no example of DOG being manufactured on a large scale industrially.
It was still small-scale manufacturing at the laboratory level. That is, the manufacturing method is a method in which so-called reagent-grade HPA is used as a raw material to react with 'I'' MP, and in this case, the yield of DOG is high when calculated based on HPA standards, and there is no problem at first glance. I can see it.

However, in order to produce DOG on an industrial scale, it is necessary to consistently consider the aldol condensation reaction of isobutyraldehyde (hereinafter referred to as IBA) and formaldehyde. The recovery rate at the stage of recovery is low, and the yield of DOG based on IBA or formaldehyde is extremely low. The present invention solves these drawbacks, and
H obtained by aldol condensation of BA and formaldehyde
This method involves reacting TMP with a PA-containing reaction product solution or a solution from which unreacted IBA present in the reaction product solution has been distilled off, and does not include an HPA recovery step, so the DOG yield based on IBA or formaldehyde is Extremely high and efficient.

The reaction between IBA and formaldehyde can be carried out under known reaction conditions in the presence of an alkali catalyst such as an amine or an alkali carbonate, and the reaction product liquid obtained by this reaction contains HPA, unreacted IBA, formaldehyde, methanol, formate,
Contains neopentyl glycol, water, alkaline catalyst, etc. Apply TM directly to mixed liquids containing various impurities.
It was predicted that when adding P and stirring the reaction, highly pure DOG would not be obtained due to the influence of these impurities. Furthermore, when adjusting the amount of acid catalyst added during the reaction of HPA and TMP, it is not necessary to take into account the neutralization of the alkali catalyst used during aldol condensation, and highly pure DOG can be obtained.

TMP is added in the form of solid crystals, in a molten state, or in a state dissolved in water or a solvent.

The reaction between HPA and TMP is a so-called acetalization reaction, and an acid catalyst is used as the catalyst.

The acid catalyst is not particularly limited, but mineral acids such as hydrochloric acid and phosphoric acid, or organic acids such as P-)luenesulfonic acid and methanesulfonic acid are generally useful. The amount of acid catalyst added varies depending on the type of acid catalyst, but when hydrochloric acid is used, it is 2 to 6% by weight based on the amount of TMP charged, and when P-)luenesulfonic acid is used, it is 8 to 12% by weight. % is suitable.

The reaction temperature is preferably in the range of 35 to 60°C.

Below 35°C, the reaction rate is too slow to be industrially practical, and problems arise particularly with the solubility of HPA.

Furthermore, at temperatures above 60°C, the amount of side reaction products produced increases, making it impossible to obtain highly pure DOG.

The reaction time is preferably about 3 to 5 hours, and there is no particular restriction on the pressure, but industrially it may be carried out under normal pressure. j Uri is practical.

With respect to HPA present in the aldol reaction product solution, the amount of TMP charged is HPA:TMP=0.

95-1.15:1, preferably HPA:TMp=1.
The range is from 05 to +, +o:+. When it is out of this range, the amount of side reaction products produced increases and highly pure DOG cannot be obtained.

The acetalization reaction method in the present invention can be carried out in any of the continuous, semi-continuous, and batch methods. For example, in the case of a continuous type, IB is prepared in a separate reaction vessel in the presence of a basic catalyst.
The process was carried out while continuously charging the (PA) reaction product liquid obtained by carrying out the aldol condensation reaction of A and formaldehyde, TMP and the acid catalyst into an acetal reaction vessel.

In general, the method of charging the acid catalyst is to directly use the aldol reaction product solution with the HPA source and 1- in the present invention as the acid is, or the reaction product solution after distilling off unreacted IBA to perform the HPA recovery step. In addition, it is possible to eliminate the loss of HPA that occurs when the recovery step is introduced, and as a result, high yield and high purity DOG can be obtained from a simplified process. I can do it.

In the Examples and Comparative Examples below, "96" and "parts" mean "% by weight" and "parts by weight", respectively, unless otherwise specified.

Example 1 IBA)-d= using triethylamine as a catalyst
HPA64 obtained by reacting tremaldehyde.

3296 (0.589+S mol), IBAl. +.

%, methanol 4.0896,) Liepuramine 2
, 57% water, 26.53% water, 1.40% indivisible, 93.5 parts of HPA reaction product solution, 182° 5 parts of TMP aqueous solution dissolved in 110.0 parts, and 5 parts of hydrochloric acid (5596) as a catalyst. Mix 0 parts and heat at 55°C under normal pressure.
．． The reaction was carried out for 0 hours.

About 0.5 hours after the start of the reaction, a part of the produced OG crystallized, and the reaction liquid became cloudy and slurry-like.

This state becomes noticeable as the reaction progresses, and 7.0
After some time, the stirring efficiency was reduced.

After the reaction, add 10% aqueous sodium carbonate solution to adjust the pH of the reaction solution.
Neutralization was carried out until the value was 7.2.

After neutralization, DOG produced according to the usual t11 parts PJF method was separated as a cake, and after drying 113.1 parts (0
, 5184 mol) of DOG was obtained as a product.

The yield determined from this obtained amount corresponds to 85.9 mol% on an IBA basis and 96.0 mol% on a TMP basis.

Further, as a result of analyzing the product, it was found to be of high quality as shown in Table 1.

Example 2 Unreacted IBA was recovered from the HPA reaction product solution obtained in the same manner as in Example 1 by a distillation method, HPA70.6
HPA with a composition of 7% ([], 5889 mol), IBAo, 02%, methanol 1.40%, triethylamine 1.84%, water 20.70%, and unknowns 0.9796.
Example 1 except that 8560 parts of the reaction product liquid was used as the HPA source
I) OG was produced under the same operation and conditions as in .

After drying, 3.3 parts (0.5191 mol) of M DOG was obtained as a product.

Yield 1'i IBA 86.0 mol%, TMP
This corresponds to 96.1 mol% on a standard basis.

Further, as a result of analysis of this product, it was found to be of high quality as shown in Table 1.

Example 3 P-)luenesulfonic acid 1 as a 7cetalization reaction catalyst
DOG was produced using the same operations and conditions as in Example 1, except that 9.1 parts of aqueous salt was used.

After drying, 2.0 parts of M (0,5134 mol) of DOG was obtained as a product.

The yield corresponds to 85.0 mol% based on IBA.

Further, as a result of analysis of this product, it was found to be of high quality as shown in Table 1.

Example 4 HpA 51.81% (21,968 mol) in which CIBA and formaldehyde were reacted using potassium carbonate as a catalyst, IBAI, +096, methanol 2.6396,
Formaldehyde 1°50%, potassium formate 2.029
6, Neopentyl Glycol 2, 5396, Water 66.
DOG was produced under the same operations and conditions as in Example 1, except that 47,325 parts of the HPA reaction product liquid having a composition of 78% and 1.65% of unknowns was used as the HPA source.

After drying 4308.7 parts (19,749 mol) of l) O
G was obtained as a product.

The yield was 83.4 mol% based on IBA, and 98% based on TMP.
This corresponds to +7 mol%.

Further, as a result of analysis of this product, it was found to be of high quality as shown in Table 1.

Comparative Example 1 150 parts of water was added to the HPA reaction product liquid obtained in the same manner as in Example 1, and while stirring and cooling, HPA (substantially HPAf polymer) was crystallized. The crystallized HPA was separated by a conventional method, and a cake containing 53.6% HPA was obtained.
(0,4708 mol), IBAo, 0.03%, methanol 0.0796, triethylamine 0.01%, water 44
．． Hydrous HPA with a composition of 5% and 1.80% unknown
6 parts of 89° were obtained.

DOG was produced using the same operations and conditions as in Example 1, except that this hydrated HPA was used as the HPA source.

After drying, 90.1 parts (0,4130 mol) of DOG was obtained as a product.

Yield is 69.6 mol% based on IBA, 97% based on TMP
．． It was 0 mol%. In addition, HP from the HPA reaction product liquid
When recovering A by crystallization, if 96.5 parts of the reaction product liquid were used and less than 150 parts of water was added, the entire reaction product liquid solidified at room temperature, making it virtually impossible to carry out the r-filtration operation.

Additionally, the results of product analysis are shown in Table 1.

September 7, 1980, before the procedural amendments Commissioner of the Patent Office 1. Indication of the case 1988 Patent Application No. 9266 2. Name of the invention Process for producing dioxane glycol 6. Person making the amendment Relationship to the case Patent applicant Address 100) 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name (446) Mitsubishi Gas Chemical Co., Ltd. Representative Director
No Kazuyoshi 5, Specification of contents of amendment, page 1, 2nd line to 1st line from the bottom [DOG is.........Much (song 7 Lepur]) as follows: Correction: “DOG in the present invention is neo-yokoshin and 1.

It is a polyhydric alcohol having a 3-dioxane ring, and is a substance having the following 114 formula.

Claims (1)

[Claims] Reacting a hydroxypivalaldehyde-containing reaction product obtained by aldol condensation of isobutyraldehyde and formaldehyde, or a solution obtained by distilling off unreacted inbutyraldehyde present in the reaction product, with trimethylolpropane. Characteristic manufacturing method of dioxane glycol