JPH0138786B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to di(hydroxypropyl)allylisocyanurate represented by the formula ().

[In the formula, C ₃ H ₆ OH is a 2-hydroxypropyl group,
It is either a 3-hydroxypropyl group or a 2-hydroxyisopropyl group.] The compound of formula () is a polyfunctional compound containing a polymerizable allyl group and a reactive hydroxyl group in the same molecule, and is a polymerizable or condensed type compound. Resin raw materials, unsaturated polyester raw materials, unsaturated polyurethane raw materials, acrylate resin raw materials, reactive diluents, organic synthesis intermediates,
Agrochemical raw materials, biochemical drug raw materials, crosslinking agents, vulcanizing agents,
It is an industrially useful substance as a raw material for surfactants, paints, inks, metal surface treatment agents, chelating agents, and other materials.

The present inventors created an isocyanurate-based substance,
Many studies have been conducted on the development of applications and industrial production methods, and many results have been achieved.For allyl isocyanurates, for example, patents Nos. 281924, 282405, 311451,
No. 311452, No. 318687, and No. 518868, and part of the research was published in JP-A-53-77294 and JP-A-55-40633. This research relates to a remarkable subsequent invention, in which we succeeded in creating di(hydroxypropyl)allylisocyanurate represented by the formula (), which had not been successful until now.

Di(hydroxypropyl)allyl isocyanurate represented by the formula () can be obtained by either a method of reacting monoallyl isocyanurate with propylene oxide or trimethylene oxide or a method of hydrating triallyl isocyanurate in the presence of an acidic substance. It can be manufactured by a method.

Hereinafter, the above methods will be illustrated and explained in more detail.

(a) Method of hydrating triallylisocyanurate in the presence of an acidic substance (b) Method of reacting monoallyl isocyanurate and propylene oxide (c) Method of reacting monoallyl isocyanurate and trimethylene oxide In the method (a) or (c) above, when a monohydroxypropyl compound is separated, it can be subjected to the same reaction again to derive a compound of formula () or (). In the method of (b), if a monohydroxypropyl compound is separated as a by-product, it can be subjected to the same reaction again to derive a mixture of compounds of formulas (), (), and (). Can be done.

Each of the above reactions is carried out under appropriate reaction conditions in a gas phase, gas phase-liquid phase, or liquid phase, although a solid phase may be present in the reaction system depending on the case.

Acidic substances in the reaction (a) include inorganic acids such as sulfuric acid, phosphoric acid, polyphosphoric acid, molybutenic acid,
Use tungstic acid, heteropolyacids, Lewis acids such as boron fluoride, aluminum chloride, iron chloride, or organic acids such as trifluoroacetic acid, trichloroacetic acid, various sulfonic acids. , solid acids such as solid phosphoric acid substances, solid silicic acid substances, and ion exchange resins may be used. The reason that the reaction (a) is generally promoted in the presence of an acidic substance is that the acidic substance is first added to the allyl group of triallylisocyanurate and then hydrolyzed in many cases. In this case, depending on the acidic substance, the presence of intermediate isopropyl sulfate or isopropyl alkoxonium due to incomplete hydrolysis may be observed, as in the case of sulfuric acid, but there are also cases where this is not the case. . In any case, the allyl group ultimately becomes a hydroxypropyl group. This reaction can be carried out not only in the form of an ionic reaction but also in the form of a radical reaction, but from an industrial perspective, an ionic reaction using sulfuric acid is advantageous. The appropriate concentration of sulfuric acid is usually 50 to 98%. When using a high concentration of sulfuric acid, it is also practically advantageous to carry out the sulfuric acid addition step and the hydrolysis step in two. In this case, the reaction is carried out in a liquid phase between room temperature and 100 DEG C., and sulfuric acid is usually used in an amount of 3 to 8 moles relative to the allyl group to be reacted in terms of pure sulfuric acid. A large amount of the compound of the formula () has already been produced in the reaction mixture after the addition of sulfuric acid, but in reality, in the presence of water (in some cases) to hydrolyze the sulfuric ester still present in the system. It is important to complete the formation of the compound of formula () by heating or leaving it for a long time.

When using acidic substances other than sulfuric acid, allyl groups are often directly converted to hydroxypropyl groups, regardless of gas phase or liquid phase reactions. Therefore, in such cases, a secondary hydrolysis step is not particularly required.

In the method (c) of reacting monoallylisocyanurate with trimethylene oxide, either an acidic or basic catalyst can be used. This reaction requires a suitable solvent to bring the solid monoallylisocyanurate into sufficient contact with the low boiling trimethylene oxide. The solvent is not particularly limited, but polar solvents such as ketones, esters, nitriles, nitrates, and aprotic polar solvents are useful. Specifically, dimethylformamide, dimethylsulfoxide, N
-Those containing no active hydrogen atoms, such as methylpyrrolidone, ethylene carbonate, propylene carbonate, and acetonitrile, are used. This reaction can be carried out at room temperature to 150°C by using an appropriate catalyst.
It is carried out at ℃. Further, such reaction conditions can be similarly applied to the method (b) in which monoallyl isocyanurate and propylene oxide are reacted.
When applied to method (b), formula (), formula (),
Which compound of formula () becomes the main reaction product cannot be unambiguously determined because it changes depending on the type of catalyst and the amount used, but in general, with acidic catalysts, the compound of formula () becomes the main reaction product. A basic catalyst tends to produce a large amount of compounds of the formula (). If either compound of formula () or formula () becomes the main product, the compound of formula () will become the by-product, but if the reaction conditions are made harsher, for example, under pressure or at high temperature. and()
A compound of the formula is produced in significant amounts.

The reaction in (b) between monoallyl isocyanurate and propylene oxide proceeds based on the acidic nature of monoallyl isocyanurate itself, even under heat or pressure. It is recommended to use a catalyst. Examples of acidic catalysts include inorganic acids (e.g., sulfuric acid, hydroborofluoric acid, perchloric acid, phosphoric acid, etc.), organic acids (e.g.,
Various sulfonic acids, trihalogenoacetic acids, etc.), Lewis acids (e.g., boron phosphate, aluminum phosphate, boron fluoride, aluminum chloride, lithium borofluoride, etc.), anion exchange resins, acidic fluorides, acidic sulfates, etc. are used. , basic catalysts include alkali metal carbonates, alkali metal fluorides,
Alkali metal oxide, alkali metal hydroxide, alkali metal hydride, alkali metal alcoholate, alkali metal amide, quaternary ammonium hydroxide, tertiary amine, tertiary amide, cation exchange resin, transition metal oxide, Transition metal hydroxides and the like are used.

Di(hydroxypropyl)allylisocyanurate of the formula () obtained as described above can be purified by a distillation method and, if necessary, an adsorption treatment method, contrary to the initial expectations of the inventor. That is, in the early stages of our research with di(hydroxypropyl)allylisocyanurate, the compound of formula () would be easier to recrystallize than monohydroxypropyl diallylisocyanurate, but it would be easier to recrystallize than monohydroxypropyldiallylisocyanurate, It was expected that it would be possible. However, while investigating the properties of di(hydroxypropyl)allylisocyanurate, it was discovered that it is difficult to recrystallize in the absence of acidic, basic, or polymerization catalyst substances, and that it is difficult to recrystallize rather than recrystallize. It was found that it could be easily purified by distillation, and it was discovered that when distilled under reduced pressure at temperatures below 200°C, it could be purified without causing decomposition into oxazolidones, which was initially feared. It is. Furthermore, immediately after synthesis, di(hydroxypropyl)allyl isocyanurate of the formula () forms strong hydrogen bonds with other by-product hydroxypropyl allyl compounds and becomes an extremely viscous fluid or glass-like solid solution. It was thought that it was impossible to fractionate and purify this by adsorption, and many failures had been made. Inorganic materials (e.g. silica, alumina,
They also found that purification can be easily achieved by passing through a layer of activated carbon, silicates, heteropolyacids) or organic substances (e.g., ion exchange resins, porous resins) or by stirring in the presence of these substances. . Although such adsorbent treatment methods can be carried out under normal pressure, the purpose can be advantageously achieved by application under high pressure or reduced pressure, or an alternation of these.

The present invention has revealed a novel compound of the formula () that is equivalent to or more useful than conventional allylic isocyanurates, together with an industrially applicable production method, and di(hydroxypropyl) isocyanurate. It is noteworthy from the viewpoint of industrial applicability that the product was purified and obtained with high purity.

The present invention will be explained in more detail based on representative examples of the present invention.

Example 1 40 g of dimethylformamide, 40 g of dimethylacetamide, 16.7 g of monoallyl isocyanurate
(0.1 mol), 0.5 g of cesium fluoride, and 15.5 g (0.25 mol) of propyl oxide were placed in a pressurized reaction vessel and reacted at 100°C with stirring for 4 hours. After cooling, the reaction mixture was diluted with acetone and filtered. did.
Next, the liquid is washed with saturated saline, the organic layer is dried over anhydrous sodium sulfate, and the solvent (acetone, dimethylformamide, dimethylacetamide) is distilled and recovered. When the distillation residue was distilled using a short fractionating tube and the fraction with a distillation temperature of 130-150℃/0.05-0.07mmHg was collected, bis(2-hydroxypropyl)allylisocyanurate () and a very small amount of , bis(2-hydroxyisopropyl)allylisocyanurate (2), and 2-hydroxyisopropyl/2-hydroxypropylallylisocyanurate (23) were obtained (23 g (yield: 80%)). The product is extremely viscous and fluid. Comparison by gas chromatographic analysis with a specimen separately synthesized by the present inventor revealed that this mixture was bis(2-hydroxypropyl)allylisocyanurate ()
turned out to be the majority. This thing is
bp 140°C/0.05mmHg, and other physical properties were as follows.

Elemental analysis value C ₁₂ H ₁₉ O ₅ N ₃ (molecular weight 285.30) N calculated value 14.73%, N actual value 14.80% IR spectrum (neat); cm ^-1 3500 (O-H), 3090
(C-H of olefin), 1680 (C=0), 760 (N
-C) Example 2 100g of ethylene glycol dimethyl ether,
Monoallylisocyanurate 16.7g (0.1mol),
0.7 g of trifluoromethanesulfonic acid and 15.5 g (0.25 mol) of propylene oxide were placed in a pressurized reaction vessel and reacted at 110°C for 1 hour, then cooled.
The reaction mixture is washed with saturated brine, the organic layer is dried over anhydrous sodium sulfate, and the solvent (ethylene glycol methyl ether) is recovered by distillation. The distillation residue is distilled using a short fractionating tube, and the distillation temperature is 125℃~
If you collect the fraction at 155℃/0.04~0.07mmHg, you can obtain bis(2-hydroxypropyl)allylisocyanurate (), bis(2-hydroxyisopropyl)
18 g (yield: 63%) of a mixture of allyl isocyanurate ( ) and 2-hydroxyisopropyl/2-hydroxypropyl allyl isocyanurate ( ) are obtained. This product is an extremely viscous fluid, and gas chromatographic analysis comparing it with a standard product synthesized separately by the present inventor revealed that ()41.0%;
() 26.4% and () 32.6%.

Elemental analysis value C ₁₂ H ₁₉ O ₅ N ₃ (molecular weight 285.30) N calculated value 14.73%, N actual value 14.81% IR spectrum (neat); cm ^-1 3560 (O-H), 3090
(C-H of olefin), 1680 (C=0), 765 (N
-C) Example 3 70 g of dimethyl sulfoxide, 16.7 g (0.1 mol) of monoallylisocyanurate, 15.5 g (0.25 mol) of trimethylene oxide, and 0.5 g of lithium borofluoride were placed in a pressurized reaction vessel and heated at 90 to 95°C for 2.5 hours. After the reaction, the mixture is cooled, washed with saturated brine, extracted with methane dichloride, the extracted organic layer is separated, dried over anhydrous sodium sulfate, methane dichloride is distilled off, and the residue is fractionated under reduced pressure. Babis(3-hydroxypropyl)allylisocyanurate (),
bp150-153℃/0.07mmHg, 23g (yield approx. 91%)
get it.

Elemental analysis value C ₁₂ H ₁₉ O ₅ N ₃ (molecular weight 285.30) N calculated value 14.73%, N actual value 14.75% IR spectrum (neat); cm ^-1 3550 (O-H), 3090
(C-H of olefin), 1680 (C=0), 755 (N
-C) nmr spectrum ( _CDCl3 ); δ1.60-2.10 (q,
4H), 2.80~3.10 (broad s, 2H), 3.45~3.80
(t, 4H), 3.95~4.20 (t, 4H), 4.40~4.60
(d, 2H), 5.10-5.45 (m, 2H), 5.60-6.20
(m, 1H) Example 4 Triallylisocyanurate 100g (0.4mol)
Add 200g of 95% sulfuric acid to this while stirring at below 40℃.
(2.0 mol) was added dropwise over a period of 2 hours, the reaction was allowed to stand for 8 hours at 30-35°C, and then 400 ml of water was added and boiled for 7 hours. The reaction mixture is then neutralized by adding sodium hydroxide, the neutralized solution is extracted repeatedly with benzene, the extracts are collected, dried over anhydrous sodium sulfate, and then distilled to recover the solvent. The residue is distilled under reduced pressure at 160℃/0.5mmHg.
hydroxypropyl diallyl isocyanurate,
() is first separated. Further vacuum distillation of this residue yields bis(2-hydroxypropyl)allylisocyanurate, (), bp 140°C/0.05mmHg. The yield was 77.5g (yield approximately 68%).

In this method, the sulfuric acid concentration is less than 98%, i.e. 80-98%.
%, but if the sulfuric acid concentration is lowered, it is necessary to raise the reaction temperature or make the reaction time longer than under the above conditions. Bis(2-hydroxypropyl)allylisocyanurate, () can be purified by distillation as well as by adsorption using activated clay. It is advisable to check that it is not If there is a small amount of sulfate radicals, it is necessary to remove them in advance with barium hydroxide in order to improve the yield. The presence of unnecessary sulfate groups promotes the decomposition of () during the purification operation, which leads to a decrease in yield. If you take this precaution, even if you change the sulfuric acid concentration in various ways ()
A yield of 60% or more is promised.

The analytical values of the purified product obtained by this sulfation hydration method are as follows.

Elemental analysis value C ₁₂ H ₁₉ O ₅ N ₃ (molecular weight 285.30) N calculated value 14.73%, N actual value 14.81% IR spectrum (neat); cm ^-1 3500 (O-H), 3090
(C-H of olefin), 1680 (C=0), 760 (N
-C) nmr spectrum ( _CDCl3 ); δ1.10-1.30 (d,
6H), 3.55-4.25 (m, 8H), 4.35-4.55 (d,
2H), 5.05-5.45 (m, 2H), 5.55-6.20 (m,
1H)

Claims (1)

[Claims] 1. General formula [In the formula, C ₃ H ₆ OH is a 2-hydroxypropyl group, 3
-hydroxypropyl group or 2-hydroxyisopropyl group] di(hydroxypropyl)allylisocyanurate.