JPH0380143B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application Diallyl ether of trimethylolpropane is a useful compound used as a polyester modifier, synthetic resin raw materials, and intermediates thereof.

BACKGROUND ART Many methods have been disclosed for producing allyl etherified trimethylolpropane by reacting trimethylolpropane with allyl chloride in the presence of an alkali metal hydroxide, but none of them are industrially satisfactory. This is not the way to do it.

In the allyl etherification reaction between trimethylolpropane, an alkali metal hydroxide, and allyl chloride, trimethylolpropane first reacts with the alkali metal hydroxide to produce an alkali metal salt of trimethylolpropane and water, and then the The alkali metal salt and allyl chloride react to form an allyl etherified product and an alkali metal chloride, thereby achieving allyl etherification of trimethylolpropane. Since the above reaction occurs, the presence of water in the reaction system slows down the reaction rate, suppresses the formation of diallyl ether of trimethylolpropane, and further intensifies the hydrolysis of allyl chloride, which is a side reaction. It is disadvantageous to use aqueous solutions of alkali metal hydroxides in which water is supplied in large quantities.

In order to improve this point, a method has been disclosed in which toluene is present as an entrainer in the system to allow the reaction to proceed while removing water (Japanese Patent Application Laid-open No. 41313/1983), but this method does not complicate the process. I can't avoid it.

In addition, when a solid alkali metal hydroxide is used, the solubility of the alkali metal hydroxide in trimethylolpropane is low, and the solubility of the alkali metal salt of the trimethylolpropane produced is also low, resulting in extremely poor reactivity. Normal stirring is difficult due to the presence of solid matter. In order to improve this point, British Patent No. 821977 takes an improvement measure to prevent deterioration of stirring conditions due to precipitation of solids in the reaction mixture by dividing and alternately adding solid alkali metal hydroxide and allyl chloride. However, a solid alkali metal hydroxide must be introduced into a reaction vessel filled with vapor of allyl chloride, which requires an industrially difficult operation.

In addition, methods of using a reaction medium to make the reaction proceed smoothly, such as dimethyl sulfoxide (German Patent No. 1178840), methylpropyl ketone (Japanese Unexamined Patent Publication No. 73806/1983), allyl of polymethylolalkane, etc. Ether (British Patent No.
821977) etc. are disclosed.
However, when these methods are used, there are problems such as separation of the by-product alkali metal hydrate and recovery of the reaction medium, and they have the drawback of complicating the reaction process.

On the other hand, when an aqueous solution of alkali metal hydroxide is used, it has the above-mentioned drawbacks, but
It has advantages such as easy separation of by-product alkali metal chloride and no need to recover the reaction medium.

Therefore, JP-A-57-81418 discloses a method for obtaining a highly allylated reaction product by reacting a polyhydric alcohol and allyl chloride under phase transfer catalytic conditions. By using a mobile catalyst, the reaction proceeds smoothly even when an aqueous solution of an alkali metal hydroxide is used.

However, this method not only requires a fairly large amount of phase transfer catalyst and is economically disadvantageous, but also produces a large amount of triallyl ether during the allyl etherification reaction of trimethylolpropane, making diallyl ether the main component. This is a disadvantageous way to obtain it as a product.

Problems to be Solved by the Invention The present inventors have developed a simplified production process that does not use organic solvents and uses an aqueous solution of alkali metal hydroxide, and that achieves a high reaction rate and the production of trimethylolpropane. The present invention was completed after extensive research into a method for obtaining diallyl ether of trimethylolpropane in good yield while suppressing the formation of triallyl ether.

Means for Solving the Problem The present invention provides that, by reaction with trimethylolpropane, an alkali metal hydroxide and allyl chloride,
In the method for producing diallyl ether of trimethylolpropane, trimethylolpropane,
The molar ratio of the alkali metal hydroxide, water and quaternary ammonium salt is 1:0 to 1:0 to 9:
An aqueous solution of allyl chloride and an alkali metal hydroxide is dropped into a mixture consisting of 0.005 to 0.035, and
The present invention provides a method for producing diallyl ether of trimethylolpropane, characterized in that the total amount of water added to the reaction system is limited to a range of 1 to 10 moles per mole of trimethylolpropane.

That is, the total amount of water added to the reaction system is adjusted to a range of 1 to 10 moles per mole of trimethylolpropane, and the amount of quaternary ammonium salt to be used is adjusted by dropping the aqueous solution of allyl chloride and alkali metal hydroxide. The present invention provides a method for obtaining diallyl ether in a good yield while suppressing the formation of allyl etherified products of trimethylolpropane, especially triallyl ether, even if the amount is small.

Specific embodiments of the present invention will be described below.

As the quaternary ammonium salt used in the method of the present invention, any quaternary ammonium salt can be used without particular limitation. Examples include tetraalkylammonium halides such as tetrabutylammonium bromide and tetramethylammonium chloride; benzyltrialkylammonium halides such as benzyltrimethylammonium chloride; octyltriethylammonium chloride, todecyltrimethylammonium iodide, , hexadecyltrimethylammonium bromide, tetrabutylammonium sulfate, benzyltrimethylacetate, and the like.

The amount of the quaternary ammonium salt used is preferably 0.5 to 3.5 mol% based on trimethylolpropane.

If the amount of the quaternary ammonium salt used is less than 0.5 mol % based on trimethylolpropane, the effect will be small.

In addition, if the amount used exceeds 3.5 mol%,
Although a slight increase in the yield of diallyl ether of trimethylolpropane can be expected, the effect is not commensurate with the increase in the amount of catalyst and the production of triallyl ether of trimethylolpropane increases, so it is not economically advantageous.

Under the conditions of the present invention, the reaction temperature is 60~
The temperature is 120°C, preferably 70-110°C. If it is less than 60°C, the reaction rate will be slow, and if it exceeds 120°C, side reactions will become intense, which is not preferable.

The amount of alkali metal hydroxide used in the method of the present invention is preferably 2 to 5 moles per mole of trimethylolpropane. If the amount is less than 2 moles, the conversion rate of trimethylolpropane will be low and the yield of diallyl ether of trimethylolpropane will be low, and even if the amount exceeds 5 moles, it will not be effective in increasing the yield of diallyl ether.

The total amount of water added to the reaction system must be limited to 1 to 10 moles per mole of trimethylolpropane. If the total amount of water added to the reaction system is less than 1 mole per mole of trimethylolpropane, a large amount of solids will precipitate in the reaction system, making stirring operation extremely difficult, and if the total amount of water added to the reaction system exceeds 10 moles, allyl chloride This is not preferable because the hydrolysis of

Note that water can be introduced into the reaction system not only as water in an aqueous alkali metal hydroxide solution, but also in separate introduction of alkali metal hydroxide or an aqueous solution of alkali metal hydroxide and water. Although it is possible, it is preferable to introduce water as an aqueous solution of the alkali metal hydroxide because the operation becomes complicated.

The concentration of the aqueous alkali metal hydroxide solution used is not particularly limited as long as the amount of alkali metal hydroxide described above is used and the total amount of water added to the reaction system is controlled within the range described above. However, it is preferable to use an aqueous solution of an alkali metal hydroxide of 75% by weight or less, which is relatively easy to operate while preventing the precipitation of alkali metal hydroxide crystals and maintaining an aqueous solution state.

Next, as for the method of adding the alkali metal hydroxide, as long as the total amount of water added to the reaction system is within the range described above, a predetermined amount of the alkali metal hydroxide may be added dropwise as an aqueous solution, or a predetermined amount A part of the alkali metal hydroxide may be pre-existing in the reaction system as an aqueous alkali metal hydroxide solution, and the remaining amount of alkali metal hydroxide may be added dropwise as an aqueous solution, or a predetermined amount of alkali metal hydroxide may be added dropwise as an aqueous solution. A part of the alkali metal hydroxide may be previously present in the reaction system as a solid, and the remaining amount of the alkali metal hydroxide may be added dropwise as an aqueous solution. However, when a predetermined amount of alkali metal hydroxide is partially present in the reaction system in advance, the amount of alkali metal hydroxide is preferably equal to or less than trimethylolpropane, and the use of more than equimolar is prohibited. It is better to avoid this because the alkali metal salt of trimethylolpropane that is produced sticks to the reactor wall, causing problems in reaction operation.

Further, the dropping time of the aqueous alkali metal hydroxide solution is not particularly limited, but it is preferably equal to or shorter than the dropping time of allyl chloride.

The amount of allyl chloride used is preferably 1.8 to 2.5 moles per mole of trimethylolpropane. If it is less than 1.8 mol, the yield of diallyl ether of trimethylolpropane will be low, which is undesirable.
Even if an amount exceeding 2.5 mol is used, the yield of diallyl ether of trimethylolpropane will not increase, so it is not economically advantageous. Furthermore, it is preferable to add allyl chloride dropwise over a period of 0.5 to 5 hours; within 0.5 hours, unreacted allyl chloride will reflux violently, making it difficult to maintain the reaction temperature; I don't see any particular effect.

Effects of the Invention According to the method of the present invention, not only is it possible to proceed the reaction smoothly without using an organic solvent, but the reaction rate is also fast, and moreover, triallyl ether of trimethylolpropane can be produced as a by-product. The main product, diallyl ether of trimethylolpropane, can be obtained in good yield while suppressing the production of trimethylolpropane. Furthermore, since the reaction solution is separated into an organic layer containing the diallyl ether of trimethylolpropane, which is the main product, and an aqueous layer containing the by-product alkali metal chloride, the product can be easily separated, and the product can be easily separated. This method is industrially advantageous because the process is simplified.

Examples of the present invention are shown below.

Example 1 67 g of trimethylolpropane and 5.6 g of tetrabutylammonium bromide were placed in a 500 ml flask equipped with a stirrer, reflux condenser, thermometer and two dropping funnels and heated to 90° C. under a nitrogen stream.

120 g of a 50% by weight aqueous sodium hydroxide solution was added dropwise to the above solution kept at 90° C. over 2 hours while stirring, and 76.5 g of allyl chloride was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued at 90°C for 1 hour.
After the reaction was completed, water was added to dissolve the sodium chloride and allowed to cool at room temperature. The reaction solution separated into two phases, an organic layer and an aqueous layer, so the layers were separated and the organic layer was analyzed by gas chromatography. As a result, 17.5 g of trimethylolpropane monoallyl ether, 77.0 g of trimethylolpropane diallyl ether, and trimethylolpropane triallyl ether
5.3g was contained in the organic layer.

The amount of water added to the reaction system as a 50% by weight aqueous sodium hydroxide solution was 60 g, which corresponded to 6.7 moles per mole of trimethylolpropane.

Example 2 The same operation as in Example 1 was carried out except that 150 g of 40% by weight aqueous sodium hydroxide solution was used. As a result, trimethylolpropane monoallyl ether was obtained.
An organic layer was obtained containing 21.5 g of trimethylolpropane diallyl ether, 72.5 g of trimethylolpropane diallyl ether, and 4.8 g of trimethylolpropane diallyl ether.

The amount of water added to the reaction system as a 40% by weight aqueous sodium hydroxide solution was 90 g, which corresponded to 10 moles per mole of trimethylolpropane.

Example 3 18g of solid sodium hydroxide was placed in a reactor in advance to form a 48% by weight aqueous sodium hydroxide solution.
The same procedure as in Example 1 was carried out except that 62.5 g was added dropwise over 2 hours. As a result, 17.6 g of trimethylolpropane monoallyl ether, 78.0 g of trimethylolpropane diallyl ether, and 5.4 g of trimethylolpropane triallyl ether were obtained. g
An organic layer containing .

The amount of water added to the reaction system as a 48% by weight aqueous sodium hydroxide solution was 32.5 g, which corresponded to 3.6 moles per mole of trimethylolpropane.

Example 4 Using 0.93 g of benzyltrimethylammonium chloride instead of tetrabutylammonium bromide,
The same procedure as in Example 3 was carried out except that 54.2 g of 48% by weight sodium hydroxide was used, resulting in 24.9 g of trimethylolpropane monoallyl ether,
Trimethylolpropane diallyl ether 68.4g
An organic layer containing 5.2 g of trimethylolpropane triallyl ether was obtained.

The amount of water added to the reaction system as a 48% by weight aqueous sodium hydroxide solution was 28.2 g, which corresponded to 3.1 moles per mole of trimethylolpropane.

Example 5 134 g of trimethylolpropane and 1.86 g of benzyltrimethylammonium chloride were placed in a 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a dropping funnel with a heat insulator and heated to 90° C. under a nitrogen stream. 133.9 g of a 65.7% by weight aqueous sodium hydroxide solution kept at 70° C. was added dropwise over 2 hours to the above solution kept at 90° C. while stirring, and 145.4 g of allyl chloride was added dropwise over 3 hours. After that, the same operation as in Example 1 was carried out, and as a result, trimethylolpropane monoallyl ether was obtained.
An organic layer was obtained containing 58.8 g of trimethylolpropane diallyl ether, 128.4 g of trimethylolpropane diallyl ether, and 6.9 g of trimethylolpropane diallyl ether.

The amount of water added to the system as a 65.7% by weight aqueous sodium hydroxide solution was 45.9 g, which corresponded to 2.6 moles per mole of trimethylolpropane.

Example 6 Trimethylolpropane was added to the same apparatus as in Example 1.
67g, benzyltrimethylammonium chloride 1.86
g and 20.8 g of 48% by weight aqueous sodium hydroxide solution
was heated to 90°C under a nitrogen stream. 90℃ under stirring
70.9 g of a 48% by weight aqueous sodium hydroxide solution was added dropwise to the above solution held in the solution over 2 hours, and 72.7 g of allyl chloride was added dropwise over 3 hours. After that, the same operation as in Example 1 was carried out, and as a result, trimethylolpropane monoallyl ether 32.9
g, trimethylolpropane diallyl ether
An organic layer containing 59.6 g and 3.0 g of trimethylolpropane triallyl ether was obtained.

The amount of water added to the reaction system as a 48% by weight aqueous sodium hydroxide solution was 47.7 g, which corresponded to 5.3 moles per mole of trimethylolpropane.

Example 7 Example 6 except that the reaction temperature was changed to 105°C.
As a result of carrying out the same operation as above, an organic layer containing 33.7 g of trimethylolpropane monoallyl ether, 59.5 g of trimethylolpropane diallyl ether, and 2.8 g of trimethylolpropane triallyl ether was obtained.

The amount of water added to the reaction system as a 48% by weight aqueous sodium hydroxide solution was 47.7 g, which corresponded to 5.3 moles per mole of trimethylolpropane.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that tetrabutylammonium bromide was not added. As a result, trimethylolpropane monoallyl ether was 38.3g, trimethylolpropane diallyl ether was 35.6g, and trimethylolpropane triallyl ether was 38.3g.
1.9g was obtained.

Claims (1)

[Claims] 1. A method for producing diallyl ether of trimethylolpropane by reaction with trimethylolpropane, an alkali metal hydroxide and allyl chloride, in which the moles of each of trimethylolpropane, alkali metal hydroxide, water and quaternary ammonium salt are Ratio is 1:0~1:0~9:0.005~
0.035, an aqueous solution of allyl chloride and an alkali metal hydroxide is added dropwise to the mixture, and the total amount of water added to the reaction system is limited to a range of 1 to 10 moles per mole of trimethylolpropane. A method for producing diallyl ether of trimethylolpropane.