JPH089564B2 - Method for producing partial ether of polyol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is applicable to synthetic intermediates such as esters, urethanes, thiol compounds and water-soluble vehicles, as well as crosslinking agents, reactive diluents, modifiers and photocuring agents. The present invention relates to a novel method for producing a partial ether of a polyol useful as a raw material for a polymerizable resin.

(Problems to be Solved by the Prior Art and the Present Invention) Conventionally, an improved method of Williamson's method in which a quaternary salt coexists has been used for synthesizing full ethers of polyols (Japanese Patent Publication No. 60-39342, JP 57-81418). However, an example of selectively synthesizing a partial ether having a hydroxyl group of a polyol by these reaction methods has not been reported yet. Further, a method for synthesizing partial ethers using a bromine compound in a non-catalytic system is known (US Pat., 3.98.45).
6, J. Oil Color Chem. Assoc., 1980, 63 (12), 474-48
1). However, this reaction has drawbacks such as a long reaction time, an unfavorable yield, and a large excess amount of the bromine compound. Therefore, a method for selectively synthesizing partial ethers of polyol is desired.

(Means for Solving Problems) As a result of various investigations by the present inventors to solve the above problems, as a result of reaction between the polyol and the halogen compound, the partial ethers of the intended polyol were reduced in a short time. It was found that the yield was good and the selectivity was good.

That is, the present invention provides a polyol selected from the group consisting of trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol, and a general formula (I) R ¹ X (I) [wherein R ¹ is an alkyl group or an alkenyl group. , An aryl group or an aralkyl group, and X represents a halogen atom. ] In obtaining a partial ether of the polyol by reacting with a halogen compound represented by, the polyol and an alkali metal salt or an alkali metal hydroxide (hereinafter, the alkali metal salt and the alkali metal hydroxide are collectively referred to as An aqueous phase containing an aqueous solution containing an alkali metal salt),
These are reacted between two phases with an organic phase containing 0.3 to 1.5 mol of the halogen compound represented by the general formula (I) per 1 equivalent of the hydroxyl group of the polyol, and the reaction is carried out in the reaction system with the general formula (II). R ² OCH ₂ CH _{2 n} OR ³ (II) [In the formula, R ² and R ³ are the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and n represents a natural number. ] The compound represented by 0.002 to 0.1 mol relative to 1 equivalent of the hydroxyl group of the polyol (except when 1 part by weight or more is present per 1 part by weight of the polyol). The present invention relates to a method for producing ethers.

In the present invention, R ^{1 of the} halogen compound represented by the general formula (I) and R ² and R ^{3 of the} compound represented by the general formula (II) are used.
The alkyl group represented by is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-
Butyl, n-pentyl, iso-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, cyclopentyl, cyclohexyl group, etc., alkenyl groups include allyl, 1-butenyl, 2-butenyl, 1-
Pentenyl, 2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-decenyl, cyclopentenyl, cyclohexenyl group and the like, the aryl group is phenyl, o-methylphenyl, m-methylphenyl, p-
Methylphenyl, p-methoxyphenyl, p-nitrophenyl, pyridyl, α-picolyl, β-picolyl, γ-
Examples thereof include picolyl and naphthyl groups, and examples of the aralkyl group include benzyl, p-methylbenzyl, 2-phenylethyl, 3-phenylpropyl and naphthylmethyl groups. Specific examples of the halogen compound of the general formula (I) include methyl chloride, ethyl chloride, n-propyl chloride, iso-propyl chloride, n-butyl chloride, iso-butyl chloride and tert-chloride.
Butyl, n-pentyl chloride, iso-pentyl chloride, n-hexyl chloride, n-heptyl chloride, n-octyl chloride,
N-nonyl chloride, n-decyl chloride, n-undecyl chloride, n-dodecyl chloride, n-tetradecyl chloride, n chloride
-Hexadecyl, n-octadecyl chloride, n-eicosyl chloride, allyl chloride, 4-chloro-1-butene, 4-chloro-2-butene, 5-chloro-1-pentene, 5-chloro-2-pentene, 6- Chloro-1-hexene, 3-
Chlorocyclopentene, 3-chlorocyclohexene, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, p-chloroanisole, p-
Chloronitrobenzene, 2-chloropyridine, 2-chloro-6-methylpyridine, benzyl chloride, 1-chloro-
2-phenylethane, p-chloromethyltoluene, 1-
Examples thereof include chlorides such as chloro-3-phenylpropane and 1-chloromethylnaphthalene, and compounds in which the chlorine atom of these compounds is replaced with a fluorine atom, a bromine atom or an iodine atom. Specific examples of the compound of the general formula (II) include mono- or dimethyl ether such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having various molecular weights (molecular weight of 200 to 20,000),
Mono or diethyl ether, mono or dipropyl ether, mono or dibutyl ether, mono or dipentyl ether, mono or dihexyl ether, mono or diheptyl ether, mono or dioctyl ether, mono or dinonyl ether, mono or didecyl ether, mono Lauryl ether, monocetyl ether, monostearyl ether, monooleyl ether,
Monooctyl phenyl ether, monononyl phenyl ether, monophenyl ether, mononaphthyl ether, monobenzyl ether, monophenyl ethyl ether, lauryl methyl ether, lauryl ethyl ether, lauryl propyl ether, lauryl butyl ether, cetyl methyl ether, cetyl ethyl Ether, cetyl propyl ether, cetyl butyl ether, stearyl methyl ether, stearyl ethyl ether, stearyl propyl ether, stearyl butyl ether,
Oleyl methyl ether, oleyl ethyl ether, oleyl propyl ether, oleyl butyl ether, octyl phenyl methyl ether, octyl phenyl ether
Ethyl ether, octyl phenyl propyl ether, octyl phenyl butyl ether, nonyl phenyl methyl ether, nonyl phenyl ethyl ether, nonyl phenyl propyl ether, nonyl phenyl butyl ether, diphenyl ether, dinaphthyl ether, dibenzyl ether, diphenyl ethyl Examples thereof include ether. The amount of the compound of the general formula (II) is 0.002 to 0.1 mol, based on 1 equivalent of the hydroxyl group of the polyol,
It is preferably 0.004 to 0.05 mol, but less than 1 part by weight per 1 part by weight of polyol. The aqueous phase used in the present invention contains a polyol and an alkali metal salt. The content ratio of the alkali metal salt is not particularly limited and can be appropriately selected within a wide range, but an aqueous solution or a solid alkali metal salt is equivalent to 1 equivalent of the hydroxyl group of the polyol.
The amount used is 0.2 to 5.0 mol, preferably 0.5 to 2.0 mol. The alkali concentration of the aqueous alkali solution is not particularly limited, but is usually 20% or more, preferably 40 to 65%. A wide variety of known alkali metal salts can be used, and examples thereof include lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate. Of these, sodium hydroxide or potassium hydroxide is particularly suitable.
The organic phase contains a halogen compound, and the amount thereof is preferably 0.3 to 1.5 mol per 1 equivalent of the hydroxyl group of the polyol. The organic solvent used as the organic phase in the reaction is, for example, an inert solvent such as n-hexane, n-pentane, benzene, toluene, xylene, tetrahydrofuran, dioxane or a diether of the compound represented by the general formula (II). Although a protic organic solvent can be used, the reaction can be performed in a solventless system. Further, the reaction is carried out at 25 to 90 ° C., preferably 45 to 70 ° C., under pressure or atmospheric pressure, usually for 2 to 16 hours, preferably 2
It is good to be done for 8 hours.

The target compound can be easily isolated and purified from the reaction mixture by a conventional separation method. For example, the alkali metal halide that precipitates after the reaction is separated by filtration, the aqueous phase and the organic phase are separated, and then the organic phase is distilled to separate partial ethers of the intended polyol and unreacted halogen compounds. can do. By using the method of the present invention, partial ethers of polyol can be easily obtained with good yield and good selectivity.

(Effect of the invention) As is clear from the comparative example, allyl chloride and the polyol hardly react with each other in a catalyst-free system (Comparative Example 1), and the reaction between the allyl bromide and the polyol has a low yield (Comparative Example 2). ), And when a quaternary salt (tetrabutylammonium bromide) is used as a catalyst, the selectivity of the partial allyl ether is poor (Comparative Example 3). From the above, when the reaction is carried out using the method of the present invention, partial ethers are obtained in good yield and good selectivity, which is very excellent as a method for producing partial ethers as compared with conventional methods. I understand. From the above, the method of the present invention is simple and novel as compared with the conventional method.

(Example) Below, the comparative example and the Example of this invention are given.

Comparative Example 1 Pentaerythritol 137 g (1 mol), potassium hydroxide 224.4 g (4 mol) and water 150 g are mixed to prepare an aqueous phase. 382.5 g (5 mol) of allyl chloride is added to this aqueous phase, and the mixture is reacted at 70 ° C. for 6 hours with vigorous stirring. After completion of the reaction, the organic phase and the aqueous phase are separated and the organic phase is distilled to obtain pentaerythritol triallyl ether in a yield of 3%.

Comparative Example 2 137 g of pentaerythritol (1 mol), 224.4 g of potassium hydroxide (4 mol) and 150 g of water are mixed to prepare an aqueous phase. To this aqueous phase, 484 g (4 mol) of allyl bromide is added, and the mixture is reacted at 70 ° C. for 6 hours with vigorous stirring. After the reaction,
The precipitated potassium bromide is separated by filtration, the organic phase and the aqueous phase are separated, and the organic phase is distilled to obtain pentaerythritol triallyl ether in a yield of 30%.

Comparative Example 3 Pentaerythritol 137 g (1 mol), potassium hydroxide 224.4 g (4 mol) and water 150 g are mixed to prepare an aqueous phase. The organic phase is tetrabutylammonium bromide 8.1g
(25 mmol) and 229.5 g (3 mol) of allyl chloride are mixed and prepared. Stir vigorously to mix both phases and mix at 70 ° C for 5
React for hours. After completion of the reaction, the precipitated potassium chloride was filtered off, the organic phase and the aqueous phase were separated, the organic phase was distilled, and a 1: 4 mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether was collected at 60% yield. Get at a rate.

Comparative Example 4 Pentaerythritol 137 g (1 mol), potassium hydroxide 224.4 g (4 mol) and water 150 g are mixed to prepare an aqueous phase. The organic phase is tetrabutylammonium bromide 8.1g
Prepared by mixing (25 mmol) and 382.5 g (5 mol) of allyl chloride. Stir vigorously to mix both phases and mix at 70 ° C for 5
React for hours. After the reaction was completed, the precipitated potassium chloride was filtered off, the organic phase and aqueous phase were separated, and the organic phase was distilled to obtain a 64% yield of a 1:24 mixture of pentaerythritol triallyl ether and pentaerythritol tetraallyl ether. Get at a rate.

Example 1 An aqueous phase is prepared by mixing 137 g (1 mol) of pentaerythritol, 168.3 g (3 mol) of potassium hydroxide and 112 g of water. The organic phase is diethylene glycol 2.7 g (25 mmol)
And 400 g (3.3 mol) of allyl bromide are mixed.
Both phases are mixed with vigorous stirring and reacted at 70 ° C. for 5 hours. After completion of the reaction, precipitated potassium bromide is filtered off, the organic phase and the aqueous phase are separated, and the organic phase is distilled to obtain pentaerythritol triallyl ether in a yield of 91%. bp11
4-122 ° C / 1 mmHg, iodine value 295 (theoretical value 297), OH% 6.3 (theoretical value 6.6) Example 2 136 g of pentaerythritol (1 mol), 185 g of potassium hydroxide (3.3 mol) and 123 g of water were mixed. Prepare the aqueous phase. The organic phase is diethylene glycol 2.7 g (25 mmol)
And n-heptyl bromide, 622 g (3.5 mol). Both phases are mixed with vigorous stirring and reacted at 90 ° C. for 6 hours. After completion of the reaction, precipitated potassium bromide was filtered off,
After separating the organic phase and the aqueous phase, the organic phase is distilled to obtain pentaerythritol triheptyl ether in a yield of 80%.
bp 300 ° C./0.75 mmHg, OH% 3.8 (theoretical value 4.0) Example 3 137 g (1 mol) of pentaerythritol, 200 g (5 mol) of sodium hydroxide and 133 g of water are mixed to prepare an aqueous phase. The organic phase is prepared by mixing 3.4 g (25 mmol) of diglyme, 423.5 g of allyl bromide (3.5 mol) and 400 ml of benzene. Both phases are mixed with vigorous stirring and reacted at 70 ° C. for 8 hours. After completion of the reaction, the precipitated sodium bromide is filtered off, the organic phase and the aqueous phase are separated, and the organic phase is distilled to obtain pentaerythritol triallyl ether in a yield of 85%. bp114-122 ℃ / 1mmHg, iodine value 296 (theoretical value 297), OH
% 6.4 (theoretical value 6.6) Example 4 134 g (1 mol) of trimethylolpropane, 160 g (4 mol) of sodium hydroxide and 107 g of water are mixed to prepare an aqueous phase. The organic phase is 2.7 g (25 mmol) diethylene glycol, 290 g (2.4 mol) allyl bromide and 400 ml dioxane.
Are prepared by mixing. Stir vigorously to mix both phases, 70
React at 8 ° C. for 8 hours. After the reaction was completed, the precipitated sodium bromide was filtered off, the organic phase and the aqueous phase were separated, and the organic phase was distilled to obtain 75% trimethylolpropane diallyl ether.
In a yield of bp 138-140 ° C./10 mmHg, iodine value 236 (theoretical value 237), OH% 7.9 (theoretical value 7.9) Example 5 Pentaerythritol 137 g (1 mol), potassium hydroxide 224.4 g (4 mol) and water 150 g were mixed. To prepare an aqueous phase. The organic phase is polyethylene glycol-600 15 g (25 mmol), methyl iodide 500 g (3.5 mol) and benzene 500.
Prepare by mixing ml. Stir vigorously to mix both phases,
Incubate at 60 ° C for 6 hours. After completion of the reaction, precipitated potassium iodide was filtered off, the organic phase and the aqueous phase were separated, and the organic phase was distilled to obtain 79% pentaerythritol trimethyl ether.
In a yield of bp103-104 ℃ / 12mmHg, OH% 9.5 (theoretical value
9.6) Example 6 A water phase is prepared by mixing 137 g (1 mol) of pentaerythritol, 224.4 g (4 mol) of potassium hydroxide and 150 g of water. The organic phase is diethylene glycol 2.7 g (25 mmol)
And 306 g (4 mol) of allyl chloride are mixed and prepared. Both phases are mixed with vigorous stirring and reacted at 70 ° C. for 6 hours.
After the reaction was completed, the precipitated potassium chloride was filtered off, the organic phase and the aqueous phase were separated, and the organic phase was distilled to obtain a 71% yield of a 1: 2 mixture of pentaerythritol diallyl ether and pentaerythritol triallyl ether. Get at. bp114-1
22 ℃ / 1mmHg, iodine value 275 (theoretical value 276), OH% 9.5 (theoretical value)
9.7) Example 7 An aqueous phase is prepared by mixing 137 g (1 mol) of pentaerythritol, 224.4 g (4 mol) of potassium hydroxide and 150 g of water. The organic phase is prepared by mixing 3.4 g (25 mmol) of diglyme, 306 g of allyl chloride (4 mol) and 300 ml of benzene. Stir vigorously to mix both phases and react at 70 ° C. for 12 hours. After the reaction was completed, the precipitated potassium chloride was filtered off, the organic phase and the aqueous phase were separated, and the organic phase was distilled to obtain a 60% yield of a 3: 5 mixture of pentaerythritol diallyl ether and pentaerythritol triallyl ether. Get at. b.
p.114-122 ℃ / 1mmHg, iodine value 272 (theoretical value 274), OH% 9.9
(Theoretical value 10.4) Example 8 A water phase is prepared by mixing 137 g (1 mol) of pentaerythritol, 224.4 g (4 mol) of potassium hydroxide and 150 g of water. The organic phase is prepared by mixing 3.4 g (25 mmol) of diglyme and 382.5 g (5 mol) of allyl chloride. Both phases are mixed with vigorous stirring and reacted at 70 ° C. for 5 hours. After completion of the reaction, precipitated potassium chloride was filtered off, the organic phase and the aqueous phase were separated, and the organic phase was distilled to obtain pentaerythritol diallyl ether, pentaerythritol triallyl ether and pentaerythritol tetraallyl ether 9: 1.
A 9: 1 mixture is obtained with a yield of 51%.

Continuation of front page (56) Reference JP-A-60-252440 (JP, A) JP-A-57-58637 (JP, A) JP-A-56-63935 (JP, A) JP-A-57-81418 (JP , A) JP-A-57-109738 (JP, A) JP-A-59-134743 (JP, A)

Claims (1)

[Claims] 1. A polyol selected from the group consisting of trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol and a general formula (I) R ¹ X (I) [wherein R ¹ is an alkyl group or an alkenyl group. , An aryl group or an aralkyl group, and X represents a halogen atom. ] In obtaining a partial ether of the polyol by reacting with a halogen compound represented by the following, an aqueous phase comprising an aqueous solution containing the polyol and an alkali metal salt or an alkali metal hydroxide, and 1 equivalent of a hydroxyl group of the polyol are added. On the other hand, these are reacted with each other between two phases including an organic phase containing 0.3 to 1.5 mol of the halogen compound represented by the general formula (I), and in the reaction system, the general formula (II) R ² OCH ₂ CH _{2 n} OR ³ (II) [In the formula, R ² and R ³ are the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and n represents a natural number. ] The partial ether of the polyol characterized in that 0.002 to 0.1 mol of the compound represented by the formula (1) is present in an amount of 0.002 to 0.1 mol per 1 equivalent of the hydroxyl group of the polyol (except when 1 part by weight or more is present relative to 1 part by weight of the polyol). Manufacturing method.