JPH0138113B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydroxypropyl diallyl isocyanurate, and hydroxypropyl isocyanurate is a monomer having a polymerizable allyl group, a polymerizable or condensable monomer having an active hydrogen atom, It is industrially useful as a raw material for saturated polyester components, reactive diluents, organic synthesis intermediates, agricultural chemicals or biochemical substances, heat-stable triazine compounds, and other materials.

The present inventors created an isocyanurate-based substance,
We have conducted numerous studies and achieved numerous results regarding the development of applications and the establishment of industrial manufacturing methods.・
Showa 36-4376 (Patent 281924), Nittokuko・Sho 35-7835
(Patent No. 318687), Nittokuko・Sho 38-7988 (Patent No. 318687)
311451), Nittoku Public Corporation, 1979-7990 (patent 311452), Nittoku Public Corporation, 1977-26766 (patent 518868), Nittoku Public Corporation, 1972 (patent 311452),
53-77294, Nippon Special Publication, 1982-40633, etc., but after that, he continued his research with great enthusiasm.
He has now completed an even newer and more remarkable invention. That is, the present inventors have clarified a method for producing hydroxypropyl diallyl isocyanurate, which could not be produced industrially due to its complicated synthesis and difficulty in purification and purification.

Conventionally, a method to obtain hydroxypropyl diallyl isocyanurate by ring-opening addition reaction of alkylene oxide to diallyl isocyanurate is known (USP 3332946), but ring-opening using diallyl isocyanurate, which is difficult to synthesize using this method, as a starting material The problem was that it could not be called an industrial method because it involved an addition reaction.

The present inventors conducted various studies in view of the above problems, and as a result, completed an industrially advantageous method for producing hydroxypropyl diallylisocyanurate. That is, the present invention is characterized in that one allyl group of triallylisocyanurate is hydrated. In the present invention, different types of hydroxypropyl diallyl isocyanurate can be obtained depending on whether triallyl isocyanurate is hydrated in an aqueous sulfuric acid solution or via hydroboration. . Furthermore, the structure of the hydroxypropyl group differs depending on whether the reaction conditions are ionic or radical.
Specifically, the following compounds () or () can be obtained.

The reaction of hydrating triallylisocyanurate in an aqueous sulfuric acid solution is as follows.

When triallylisocyanurate is reacted with an aqueous sulfuric acid solution, monosulfuric acid adducts, disulfuric acid adducts, and trisulfuric acid adducts are generally obtained. Keep the sulfuric acid concentration moderate and the reaction temperature below 100°C, preferably 90°C.
If the temperature is limited to below ℃, the amount of monosulfuric acid adduct produced will increase, so when this amount reaches its maximum, either dilute it with water to stop the reaction and then heat it.
contact with an alkaline substance (heating if necessary),
After replacing the sulfate group with a hydroxyl group, () is separated from the reaction mixture by extraction or distillation and purified. Since this reaction is carried out in an aqueous system, the addition of a phase transfer catalyst is effective, and unless a radical reaction (when a radical catalyst is added or carried out in an oxygen atmosphere) is used, ( sell. However, when the reaction is carried out under pressure of oxygen in the presence of a phase transfer catalyst, a mixture of () and () is obtained. This () and ()
Although it is possible to separate a mixture with the above, it is not industrially advantageous, so depending on the purpose (for example, when using it as a raw material for unsaturated polyester), the mixture as it is is often sufficient.

In the case of sulfuric acid addition, if the sulfuric acid concentration is lower than 50%, it is necessary to slightly raise the reaction temperature and increase the reaction time. If the length is unnecessarily long, the amount of by-products of bis(2-hydroxypropyl) monoallyl isocyanurate and tris(2-hydroxypropyl) isocyanurate will increase, so care must be taken.

The synthesis of hydroxypropyl diallyl isocyanurate by the hydroboration method of triallyl isocyanurate includes the process of adding borane BHR ₂ (R is a hydrogen atom or a hydrocarbon group) to triallyl isocyanurate, and oxidizing and hydrolyzing this. 3-hydroxypropyl diallylisocyanurate () is mainly obtained, and the reaction formula is as follows.

Various types of borane BHR ₂ can be used, but the industrially cheapest one is borane BH ₃ (this is a dimer) obtained from an alkali borohydride and a Lewis acid (for example, boron trifluoride). Since it exists in the form of diborane B ₂ H ₆ ,
(It is available as a diborane solution, but the reaction can be thought of as BH ₃ ), and when using this, borane is added to 3 moles of triallyl isocyanurate.
React 1 mol of BH ₃ and oxidize the following reactants:
It is best to hydrolyze. In this case, the amount of () produced as a by-product increases.

The reaction between triallylisocyanurate and borane proceeds smoothly in an ether solvent, for example, at a temperature of 50°C or lower, preferably 0 to 30°C, and the addition reaction mixture is mixed with, for example, an aqueous hydrogen peroxide solution, oxidized, and then hydroxylated. It is made by adding an aqueous solution of alkali or alkali carbonate and hydrolyzing it at below 100℃. In this reaction, it is undesirable to use an excessive amount of borane because it increases the amount of by-products of bis(hydroxypropyl) monoallyl isocyanurate and tris(hydroxypropyl) isocyanurate, so it is better to set the reaction conditions as mild as possible. Yield is good.

It has been clarified that the hydroxypropyl diallylisocyanurate of the present invention [which has two types () and ()] can be synthesized using the method explained above. A specific example will be shown to explain the content.

Example 1 Triallylisocyanurate 200g (0.80mol)
and 300ml of 80% sulfuric acid at 65-75℃.
The reaction mixture was stirred for about 1 hour, diluted with 500 g of ice, and then neutralized with sodium bicarbonate. The neutralized mixture was extracted with benzene, and the extract was dried over anhydrous sodium sulfate and then distilled to obtain 160 g (yield: 75%) of 2-hydroxypropyl diallylisocyanurate, a colorless viscous liquid.

Example 2 Triallylisocyanurate 100g (0.40mol)
While stirring at about 40℃, add 100g of 98% sulfuric acid to this.
(1.02 mol) was gradually added dropwise until the reaction temperature was 50°C.
Complete this without exceeding ℃.
This mixture was heated at approximately 35°C for 3 hours, then at 45-50°C.
After stirring for 1 hour, 200 ml of water was gradually added, and the mixture was further stirred at 60 to 70°C for 30 minutes. After cooling the reaction mixture to room temperature, 200 ml of water was added, and this was extracted with benzene. The extract was washed with a saturated aqueous solution of sodium bicarbonate, then water, and dried over anhydrous sodium sulfate, and then the benzene was distilled off. , followed by vacuum distillation to yield 88 g of 2-hydroxypropyl diallylisocyanurate, which is a colorless viscous liquid.
(Yield 82%) is obtained. The boiling point, melting point, IR and NMR spectra of this product were consistent with those obtained using a literature method (USP3332946).

Example 3 249 g (1.00 mol) of triallyl isocyanurate was dissolved in 300 ml of tetrahydrofuran, 16.3 g (0.43 mol) of sodium borohydride powder was added thereto, and while stirring vigorously under ice cooling, 46.4 ml of boron trifluoride etherate was dissolved. drip. After the dropwise addition was completed, the reaction mixture was stirred at room temperature for 3 hours, and then added with 85% water.
ml and then 3N-sodium hydroxide aqueous solution
115ml, then add 115ml of 30% hydrogen peroxide solution.
Complete the hydrolysis by heating to 50-60 °C for an hour. After cooling, the reaction mixture was extracted with ether and the extract was distilled to obtain 208 g (yield: 78%) of a colorless oil.
This product is 3-hydroxypropyl diallyl isocyanurate, and its properties and analytical values are as follows.

bp., 155-156℃/0.6mmHg, elemental analysis value C ₁₂ H ₁₇ N ₅ O ₄ Calculated value C53.92%, H6.41%, N15.72% Actual value C53.68%, H6.35 %, N15.69% The IR spectrum and NMR spectrum were as follows.

IR spectrum (liquid film method) cm ^-1 : 3460, 1865, 765 NMR spectrum ( _CDCl3 ) δ: 6.1 to 5.6 (2H, multiplet, CH2 _- CH = _CH2 ), 5.5 to 5.1 (4H, multiplet Line, CH2 _- CH= CH2 ), 4.5-4.4 (4H _, doublet, _CH2- CH = _CH2 ), 4.2-3.9 (2H, triplet _{, -N -} CH2- ), In addition to the above-mentioned main fraction, 9 g of a colorless oil was obtained as a sub-fraction by distillation. This thing is
It was confirmed from the IR spectrum and NMR spectrum that it was 2-hydroxydiallyl isocyanurate. It was also found that 35 g of the distillation residue was a polymer of triallyl isocyanurate.

Example 4 Triallylisocyanurate 100g (0.40mol)
was dissolved in 300 ml of dry tetrahydrofuran, and this was stirred at room temperature to dissolve 9-borabicyclo[3.
3.1] Nonane in tetrahydrofuran solution (0.5
Gradually drop 800ml (molarity). After finishing dropping,
The reaction mixture was warmed to about 50°C and stirred for 3 hours, then 25ml of water was added, followed by 50ml of 3N aqueous sodium hydroxide solution, and then 50ml of 30% hydrogen peroxide solution, and then stirred at 50-60°C for 2 hours. Stir. The reaction mixture was extracted with ether, the extract was dried, the ether was distilled off, and then distilled under reduced pressure to obtain 96 g (90% yield) of 3-hydroxydiallylisocyanurate as a colorless viscous liquid. The boiling point of this product matched that obtained in Example 3, and the IR and NMR spectra patterns also matched.

Claims (1)

[Scope of Claims] 1. A method for producing hydroxypropyl diallyl isocyanurate, which comprises hydrating one allyl group of triallyl isocyanurate. 2. The method for producing hydroxypropyl diallylisocyanurate according to claim 1, which comprises hydrating triallylisocyanurate in an aqueous sulfuric acid solution. 3. The method for producing hydroxypropyl diallylisocyanurate according to claim 1, which comprises adding borane to triallyl isocyanurate, oxidizing it, and then hydrating it.