JP2009062357A - Method for producing unsaturated ether composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an unsaturated ether composition in high efficiency at a low cost by using a polyhydric alcohol and an unsaturated halogen compound as raw materials. <P>SOLUTION: The unsaturated ether composition is produced by reacting a 2-18C polyhydric alcohol with an unsaturated halogen compound in the presence of an inorganic compound, wherein the amount of the polyhydric alcohol is ≥1.5 mol based on 1 mol of the unsaturated halogen compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a highly efficient and low-cost method for producing an unsaturated ether composition using a polyhydric alcohol and an unsaturated halogen compound.

  It is known to produce an unsaturated ether composition by reacting an unsaturated halogen compound and a hydroxyl group-containing compound. For example, the reaction between a metal alkoxide and an alkyl halide is a reaction well known as the Williamson reaction.

  In Patent Document 1, regarding production of an unsaturated allyl compound, a raw alcohol is sufficiently dehydrated with a solvent that azeotropes with water until it is substantially anhydrous, and then a metal alkoxide is blended to form a metal alcoholate. A method for producing an allyl alcohol compound or a methallyl alcohol compound by removing by-produced alcohol by distillation and then reacting with allyl or methallyl halide is disclosed.

  Patent Document 2 discloses an excess amount of organic halogen from a reaction mixture obtained by reacting an alkali metal alcoholate of a polyoxyalkylene compound obtained by reacting a polyoxyalkylene compound with an alkali metal compound and an organic halide. In the method for obtaining an etherified polyoxyalkylene compound by removing an inorganic salt produced by the reaction and the reaction, water or water and an inorganic alkali are added to the reaction mixture to change an excess amount of the halide to an alcohol. At the same time, it is disclosed that the by-product inorganic salt is an aqueous solution and both are removed from the reaction mixture by liquid-liquid separation.

  Patent Document 3 discloses a glycol allyl etherification method in which dioxane is used as a solvent and glycol and an allyl halide compound are simultaneously supplied in the presence of potassium hydroxide.

  These disclosed methods are industrially implemented such as using alkali metal alcoholates that are highly reactive with water and difficult to handle, or converting excess to alcohols while using excessive raw material halides. Has the problem of cost.

  Moreover, although the said problem is eliminated by using a solvent, the process of collect | recovering the used solvent is required for implementing industrially, and the further highly efficient manufacturing method is desired.

Japanese Patent Laid-Open No. 62-39537 Japanese Patent Laid-Open No. 4-122728 Former Soviet Patent No. 1447809

  An object of the present invention is to provide a method for producing an unsaturated ether composition efficiently and at low cost using a polyhydric alcohol and an unsaturated halogen compound as raw materials.

The present inventor has made various investigations on the production method of an unsaturated ether composition using an unsaturated halogen compound and a polyhydric alcohol as raw materials. By reacting with an excess of polyhydric alcohol, the unsaturated glycol can be obtained in a high yield. It was found that ether was obtained. Furthermore, it was found that by reusing all or part of the polyhydric alcohol recovered in the purification step of unsaturated ether as a raw material, it is possible to reduce the loss of the raw material and to manufacture at a low cost. The invention has been completed.
That is, the following method was invented as means for solving the above-mentioned problems.
1) Polyhydric alcohol represented by the following general formula (1) and HO— (A—O—) n—H (1)
(In formula, n represents the number of 1-4. A is a C2-C18 alkylene group which may have a substituent, and a substituent represents an alkyl group and a hydroxyl group.)
Unsaturated halogen compound represented by the following general formula (2) and RX (2)
(In the formula, R represents an alkenyl group, and X represents a halogen.)
In the method for producing an unsaturated ether composition comprising at least one unsaturated ether compound having a hydroxyl group, using an alkali metal and / or alkaline earth metal inorganic compound (IN) exhibiting basicity, The manufacturing method of the unsaturated ether composition characterized by using the said polyhydric alcohol (1) 1.5 mol or more with respect to 1 mol of unsaturated halogen compounds (2).

  2) The unsaturated ether composition comprises a monounsaturated ether (M) having one unsaturated ether group and a diunsaturated ether (D) having two unsaturated ether groups, M) is 100 mass parts, (D) is a mass ratio of 0.01-25 mass parts, The manufacturing method of the unsaturated ether composition of 1) description characterized by the above-mentioned.

  3) The method for producing an unsaturated ether composition according to 1) or 2), wherein the unreacted polyhydric alcohol (1) is recovered and reused at least partially as a raw material.

  4) The method for producing an unsaturated ether composition according to 1) to 3), which comprises a step of removing the precipitated alkali metal and / or alkaline earth metal halide.

  5) The unsaturated ether composition according to 1) to 4), wherein the unsaturated halogen compound is one or two selected from (meth) allyl chloride and / or (meth) allyl bromide. Production method.

  6) The method for producing an unsaturated glycol ether composition according to 1) to 5), wherein the polyhydric alcohol (1) is (poly) alkylene glycol.

  7) The method for producing an unsaturated ether composition according to 1) to 6), wherein the inorganic compound (IN) is an alkali metal hydroxide.

8) The method for producing an unsaturated ether composition according to 1) to 7), which comprises the steps a) to f) described below.
a) The 1st reaction process using the said inorganic compound (IN), the said polyhydric alcohol (1), and / or the collection composition from the following collection process.
b) Moisture reduction step performed simultaneously with the first reaction step and / or after the completion of the first reaction step c) Reacting the low water content composition obtained in the moisture reduction step with the unsaturated halogen compound (2) A second reaction step.
d) A solid-liquid separation step of separating the reaction composition obtained in the second reaction step into a solid precipitate containing an alkali metal and / or alkaline earth metal halide and a solution containing an unsaturated ether compound.
e) A separation step of separating the solution containing the unsaturated ether compound obtained in the solid-liquid separation step into an unsaturated ether composition and a recovered composition containing a polyhydric alcohol.
f) A recovery step in which part or all of the recovered composition obtained in the separation step is used in the first reaction step.

9) The method for producing an unsaturated ether composition according to 1) to 7), which comprises the following steps g) to k).
g) A reaction composition containing an unsaturated ether composition using the inorganic compound (IN), the polyhydric alcohol (1) and / or a composition recovered from the following recovery step and the unsaturated halogen compound (2). Reaction process to obtain a product.
h) A moisture reduction step of obtaining a low moisture content composition by reducing the contained moisture from the reaction composition obtained in the reaction step.
i) A solid-liquid separation step in which the low water content composition is separated into a solid precipitate containing an alkali metal and / or alkaline earth metal halide and a solution containing an unsaturated ether compound.
j) A separation step of separating the solution containing the unsaturated ether compound obtained in the solid-liquid separation step into an unsaturated ether composition and a recovered composition containing a polyhydric alcohol.
k) A recovery step in which part or all of the recovered composition obtained in the separation step is used in the reaction step.

  10) Unsaturated ether composition obtained by the manufacturing method of said 1) -9) description.

  According to the present invention, an unsaturated ether composition can be produced from a polyhydric alcohol and an unsaturated halogen compound in a high yield, and at an inexpensive and industrially simple method.

  Hereinafter, the manufacturing method of the unsaturated ether composition concerning this invention is demonstrated in detail.

The present invention relates to a polyhydric alcohol represented by the following general formula (1) and H-O- (A-O-) n-H (1).
(In formula, n represents the number of 1-4. A is a C2-C18 alkylene group which may have a substituent, and a substituent represents an alkyl group and a hydroxyl group.)
Unsaturated halogen compound represented by the following general formula (2) and RX (2)
(In the formula, R represents an alkenyl group, and X represents a halogen.)
In a method for producing an unsaturated ether composition containing at least one unsaturated ether compound having a hydroxyl group by reacting with an alkali metal and / or alkaline earth metal inorganic compound (IN) exhibiting basicity, In the method for producing an unsaturated ether composition, 1.5 mol or more of the polyhydric alcohol (1) is used per 1 mol of the unsaturated halogen compound (2).

  The unsaturated ether composition includes a monounsaturated ether (M) having one unsaturated ether group and a diunsaturated ether (D) having two unsaturated ether groups, (M) Is a mass ratio of 0.01 to 25 parts by mass with respect to 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.01 to 15 parts by mass, Preferably it is 0.01-10 mass parts, Most preferably, it is 0.01-5 mass parts, Most preferably, it is a mass ratio of 0.01-3 mass parts. In the polyhydric alcohol (1), a (poly) alkylene glycol having 2 to 18 carbon atoms is preferable, more preferably a (poly) alkylene glycol having 2 to 8 carbon atoms, and still more preferably 2 to 4 carbon atoms. (Poly) alkylene glycol is mentioned. Examples of the (poly) alkylene glycol include glycols such as ethylene glycol, propylene glycol, isobutylene glycol, butylene glycol and styrene glycol, and dialkylenes such as diethylene glycol, dipropylene glycol, diisobutylene glycol, dibutylene glycol and distyrene glycol. Glycols, polyalkylene glycols such as triethylene glycol and tetraethylene glycol, and most preferred are ethylene glycols having 2 carbon atoms. In addition, polyols such as glycerin, polyglycerin, and trimethylolpropane are also preferably used.

  The polyhydric alcohol (1) to be newly used can be used as long as it has a commercially available purity, but the purity is preferably 98% by mass or more, more preferably 99% by mass or more. When alcohol is used, it may be used after increasing its purity by a known method such as distillation or dehydrating agent treatment.

  The recovered composition described later can be used alone or mixed with the newly used polyhydric alcohol (1) without further purification such as removal of the dissolved alkali metal salt.

  The amount of the polyhydric alcohol (1) is such that the polyhydric alcohol (1) is 1.5 to 10 mol, preferably 3 to 8 mol, more preferably 1 mol of the unsaturated halogen compound (2). 4 to 6 moles. When the amount of the polyhydric alcohol (1) is reduced, an unsaturated ether composition having a high ratio of a diunsaturated ether compound in which two molecules of an unsaturated halogen compound are added to one molecule of the polyhydric alcohol (1) is obtained. When the amount of the polyhydric alcohol (1) is increased, the unsaturated ether having a high ratio of monounsaturated alkylene ether (M) in which one molecule of the unsaturated halogen compound (2) is added to one molecule of the polyhydric alcohol (1). Is obtained. However, when the amount is too small, the amount of the diunsaturated ether compound (D) is excessive, which is not preferable. When the amount is too large, the equipment for manufacturing the target unsaturated ether composition becomes large, which is not preferable because the manufacturing cost increases.

  R in the unsaturated halogen compound (2) is an alkenyl group having 2 to 6 carbon atoms, preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 4 carbon atoms, and most preferably. Is an isobutylene group. Further, the halogen X is preferably a chlorine atom or a bromine atom, and in particular, a chlorine atom is preferred because it is easily available industrially and is excellent in reactivity and handling.

  The alkali metal and / or alkaline earth metal inorganic compound (IN) showing basicity (hereinafter sometimes referred to as inorganic compound (IN)) is not particularly limited as long as the aqueous solution is an inorganic compound showing basicity. Rather, alkali metal or alkaline earth metal hydroxides, carbonates, and hydrogen carbonates are preferred. In particular, alkali metal hydroxides such as sodium and potassium, alkaline earth metal hydroxides such as calcium, carbonates and hydrogen carbonates are preferable, and alkali metal hydroxides such as sodium and potassium are most preferable.

  The amount of the inorganic compound (IN) is such that the total valence of the inorganic metal is 0.5 to 2.0 mol, preferably 0.9 to 1 with respect to 1 mol of the unsaturated halogen compound (2). 0.5 mol, more preferably 1.0-1.2 mol. For example, when the inorganic compound is only an alkaline earth metal compound, the molar ratio of the inorganic compound (IN) to the unsaturated halogen compound (2) is 0.25 to 1.0, 0, respectively. 45 to 0.75 and 0.5 to 0.6.

  The inorganic compound (IN) may be used as it is or may be dispersed in a dispersion medium. When using a dispersion medium, it is preferable to use water and / or the polyhydric alcohol (1) used for the reaction (including the recovered composition obtained in the separation step described later).

  When water is used as a dispersion medium, the mass of water is preferably less than the mass of the polyhydric alcohol (1) used in the reaction, and 100 mass when expressed in terms of mass ratio with the polyhydric alcohol (1). % Or less, preferably 75% by mass or less, more preferably 50% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.

  When the polyhydric alcohol (1) is used as a dispersion medium, the polyhydric alcohol (1) used as a dispersion medium is added to the unsaturated halogen compound (2) separately from the polyhydric alcohol (1). It is necessary to adjust the total amount of the alcohol (1) so that the predetermined ratio is obtained.

  The term “dispersed in the above-mentioned dispersion medium” means a state in which the entire amount or a part of the inorganic compound (IN) is dissolved or mixed without being dissolved at all.

  As a form of mixing the polyhydric alcohol (1) and the inorganic compound (IN), they may be charged all at once, the order of mixing is not particularly limited, and even if the whole amount is added at once, It may be added intermittently in several times or continuously over a long time.

  Monounsaturated ether (M) obtained by using the inorganic compound (IN), the polyhydric alcohol (1), and the unsaturated halide (2) and having at least one unsaturated ether group A reaction product comprising a diunsaturated ether (D) having two unsaturated ether groups, an unreacted polyhydric alcohol (1), and an inorganic metal halide, a solid-liquid separation step and a separation step Is separated into a solid precipitate containing an alkali metal and / or alkaline earth metal halide and a solution containing an unsaturated ether compound, and a recovered composition containing at least unreacted polyhydric alcohol (1).

  The solid-liquid separation method is not particularly limited, and examples thereof include pressure filtration and centrifugation. In addition, when a solid-liquid separation step is provided before the separation step, since the unsaturated solid composition is contained in the separated solid, washing is performed using the polyhydric alcohol (1) used as a raw material. Is preferred. The use of the recovered composition as a cleaning solvent is particularly preferred because elution of the alkali metal halide contained in the solid matter into the cleaning liquid is suppressed.

  The liquid after washing is separated into an unsaturated ether composition and the recovered composition by the same operation as in the separation step, and is used in the separation step together with the reaction composition, combined with the recovered composition, etc. It is used effectively by using it as a reaction raw material or combining these.

  The separation step is not particularly limited as long as it can separate the target unsaturated ether composition, such as distillation, crystallization, and extraction. Before performing the separation step, the low water content reaction composition obtained through the moisture reduction step described later is separated into an unsaturated ether composition and a recovered composition containing unreacted polyhydric alcohol by distillation. It is preferred to obtain a saturated glycol ether composition.

As distillation conditions, from the viewpoint of the thermal stability of the target unsaturated ether composition, the distillation bottom temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower. Particularly preferably, it is carried out at 130 ° C. or lower.
In this process, in order to remove the low-concentration low-boiling components, for example, water, in order to increase the purity of the unsaturated ether composition, the distillation column is held at the total reflux, and the low-boiling components are concentrated in the reflux tank. When the components in the tank are stabilized, the low boiling point component may be removed by a method of extracting the liquid in the tank in a short time. By repeating this operation a plurality of times, the low boiling point component can be further removed. The time for holding at the total reflux varies depending on the distillation equipment, but it is preferable to make it longer than the time for distilling twice the amount of liquid in the reflux tank from the top of the column. Further, when the product fraction and the high boiling fraction are sufficiently separated and the product is recovered in a high yield, it is effective to perform the same operation.

  The recovered composition containing the unreacted polyhydric alcohol obtained in the separation step may be further purified by distillation or the like, but in the practice of the present invention, the recovery step is particularly subjected to a treatment such as purification. In this case, a part or all of the amount can be used as a raw material for the reaction process, which is simple and highly efficient. For example, you may use the polyhydric alcohol containing the dissolved salt obtained as a distillation residue as a raw material of a reaction process as it is. Polyhydric alcohol may be newly added to the recovered composition as needed, and obtained from other recovered facilities, for example, other manufacturing facilities producing the same type of unsaturated ether composition You may mix with collection | recovery compositions etc.

  In one of the more preferred embodiments, the moisture reduction step of reducing the moisture present in the system before the solid-liquid separation step or the separation step to obtain a low water content composition is carried out.

  The method of reducing the water content is not particularly limited, and methods such as addition of a desiccant such as zeolite or molecular sieve, distillation or distillation with an oil-water separator, etc. can be mentioned. From the viewpoint of separation efficiency and cost, distillation or oil-water separation Distillation using a vessel is preferred.

  As the degree of moisture reduction, the moisture concentration in the treatment liquid is preferably 5% by mass or less, more preferably 3% by mass or less, 1% by mass, and further preferably 0.5% by mass or less. Especially preferably, it is 0.1 mass% or less, Most preferably, it is 0.05 mass% or less. However, if the water content is 0.0005% by mass or less, the productivity is remarkably lowered, so it is desirable to stop at a higher concentration.

  Hereinafter, Method A and Method B, which are more preferable methods for producing an unsaturated glycol ether composition, will be described for each step.

(Method A)
Method A is a first reaction step in which the inorganic compound (IN) and the polyhydric alcohol (1) are reacted, and a reaction product obtained in the first reaction step is reacted with the unsaturated halogen compound (2). It has the 2nd reaction process to be made, It is characterized by the above-mentioned.

(First reaction step)
In the first reaction step, it is necessary to mix the inorganic compound (IN) and the polyhydric alcohol (1) at the above ratio.

  The reaction temperature in the first reaction step varies depending on the types and amounts of the polyhydric alcohol (1) and the inorganic compound (IN), but is usually room temperature to 180 ° C, preferably 50 to 150 ° C, more preferably 70-140 ° C.

  The pressure in the first reaction step may be any of reduced pressure, normal pressure, and pressurized, and the reaction time is not particularly limited, and the time during which the conversion rate of the inorganic compound is sufficiently high under the reaction conditions. Should be set.

(Moisture loss process)
By using the low water content reaction composition obtained by applying this step, the operation in the separation step is facilitated, and a high-purity unsaturated glycol ether composition is obtained in a high yield. In one reaction step, it is preferable to carry out one or more times between the first reaction step and the second reaction step or between the second reaction step and the separation step. More preferably, it is carried out at the same time as the first reaction step or between or both of the first reaction step and the second reaction step, most preferably simultaneously with the first reaction step. .

(Second reaction step)
In the second reaction step, it is necessary to mix the reaction product obtained in the first reaction step and the unsaturated halogen compound (2).

  The form in which the unsaturated halogen compound (2) is added to the reaction product obtained in the first reaction step may be added all at once, or may be added intermittently in multiple portions. Alternatively, it may be added continuously over a long period of time.

  The reaction temperature in the second reaction step varies depending on the types of the polyhydric alcohol (1) and the unsaturated halogen compound (2) and the type and amount of the inorganic compound (IN), but is usually 40 to 150 ° C. Yes, preferably 50-100 ° C, more preferably 55-75 ° C.

  The pressure in the second reaction step may be any of reduced pressure, normal pressure, and increased pressure, but it is usually simple and inexpensive to carry out under normal pressure. Further, the reaction time is not particularly limited, and a time during which the conversion rate of the raw material unsaturated halogen compound is sufficiently high under the reaction conditions may be set.

(Solid-liquid separation process)
The step of removing alkali metal and / or alkaline earth metal halide precipitated by solid-liquid separation is preferably performed at least once between the second reaction step and the recovery step. For example, the second reaction step You may divide and implement in multiple times like after and after a separation process. Moreover, since the precipitation amount of the halide increases when water is removed from the reaction composition, it is more preferable to carry out a step of separating the salt after carrying out the moisture reduction step. In the present invention, since the alkali metal and / or alkaline earth metal halide may be dissolved, the solid-liquid separation step is performed once between the second reaction step and the separation step. Simple and preferred embodiment.

(Separation process)
Under the above-mentioned conditions, it is separated into a recovered composition containing an unsaturated ether compound and a polyhydric alcohol (1), and the recovered composition is used in the next recovery step.

(Recovery process)
Since the recovered composition can be used as a washing liquid in the first reaction step or the solid-liquid separation step without further purification or the like, the polyhydric alcohol used in excess in the reaction step (1) is used without waste.

  By carrying out under the above conditions, a reaction composition containing an unsaturated ether composition by Method A is obtained.

(Method B)
Method B is characterized by subjecting the reaction composition obtained by reacting the polyhydric alcohol (1), the unsaturated halogen compound (2), and the inorganic compound (IN) to a moisture reduction step. Hereinafter, the method B will be described for each step.

(Reaction process)
In the reaction step, the polyhydric alcohol (1), the unsaturated halogen compound (2), and the inorganic compound (IN) are mixed at the above ratio, and the reaction includes an unsaturated ether composition by one reaction. It is a process of obtaining a product.

  The polyhydric alcohol (1), the unsaturated halogen compound (2), and the inorganic compound (IN) are mixed in the form of the unsaturated halogen compound (2) and the inorganic compound (IN) in the presence of the polyhydric alcohol (1). It is preferable to mix the inorganic compound (IN), and it is more preferable to add the unsaturated halogen compound (2) to the mixture of the polyhydric alcohol (1) and the inorganic compound. The unsaturated halogen compound (2) is added to the mixture of the polyhydric alcohol (1) and the inorganic compound (IN) in the form of adding the whole amount at once, but in a plurality of times. Or may be added continuously over a long period of time.

  The reaction temperature varies depending on the types of the polyhydric alcohol (1) and the unsaturated halogen compound (2) and the type and amount of the inorganic compound (IN), but is usually 40 to 150 ° C., preferably 50 to It is 100 degreeC, More preferably, it is 55-75 degreeC.

  The pressure in the reaction step may be any of reduced pressure, normal pressure, and increased pressure, but it is usually simple and low-cost to be performed under normal pressure.

  The reaction time is not particularly limited, and a time during which the conversion rate of the raw material unsaturated halogen compound is sufficiently high under the reaction conditions may be set.

  By performing the reaction under the above conditions, a reaction composition containing an unsaturated ether composition can be obtained.

(Moisture loss process)
As the degree of moisture reduction in the moisture reduction step of the reaction composition, the moisture concentration in the treatment liquid is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass. It is 0.5 mass% or less, Especially preferably, it is 0.1 mass% or less, Most preferably, it is 0.05 mass% or less. However, if the water content is 0.0005% by mass or less, the productivity is remarkably reduced or the amount of unsaturated ether loss is increased.

(Solid-liquid separation process)
The recovery step in Method B can be carried out by the same operation as in Method A. It is preferable to perform the step of removing alkali metal and / or alkaline earth metal halide precipitated by solid-liquid separation between the reaction step and the recovery step at least once, for example, after the reaction step and the separation step You may divide and implement in multiple times like later. In addition, since the precipitation amount of the alkali metal and / or alkaline earth metal halide increases when water is removed from the reaction composition, the subsequent work can be performed by performing the solid-liquid separation step after the moisture reduction step. Can greatly improve the performance. In the present invention, since alkali metal and / or alkaline earth metal halides may be dissolved, it is convenient to carry out the solid-liquid separation step once between the moisture reduction step and the separation step. And is one of the preferred embodiments.

(Separation process)
The separation step in Method B can be carried out in the same manner as in Method A, except that the low water content reaction composition obtained in the moisture reduction step is used.

(Recovery process)
The recovery step in Method B can be carried out by the same operation as in Method A.

By carrying out under the above conditions, a reaction composition containing an unsaturated ether composition by Method B is obtained.
As the merit by the method A, since it is not necessary to carry out the water loss step after the second reaction step, there is no loss of unsaturated ether, and it can be produced in a high yield. On the other hand, the merit in the method B The loss of polyhydric alcohol is less than that of A. Therefore, an advantageous method may be selected depending on the situation.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, for convenience, “parts by mass” may be simply referred to as “parts”.
The above analysis was performed using the following apparatus.
Gas chromatography apparatus: GC-15A manufactured by Shimadzu, J & W capillary column DB-1 (0.53 mmφ × 30 m)
Conditions: Holding at 40 ° C. for 5 min, heating at 10 ° C./min, holding at 200 ° C. for 5 min Moisture content measuring device: MK-510 manufactured by Kyoto Electronics Industry Co., Ltd. (KEM)
Standard sample: Karl Fischer SS manufactured by Mitsubishi Chemical Corporation
Example 1
Production of ethylene glycol methallyl ether using new ethylene glycol (reaction process)
A 3 L flask was charged with 1500.0 g (24.17 mol) of ethylene glycol, 420.92 g of 48% by weight aqueous sodium hydroxide (5.05 mol of NaOH), and 452.79 g (5.00 mol) of methallyl chloride. The reaction was carried out at 3 ° C. for 3 hours and then at 70 ° C. for 3 hours. Solid precipitation was observed in the flask. The yield of ethylene glycol monomethallyl ether at the end of the reaction was 85.6 mol% based on the raw material methallyl chloride. The yield of ethylene glycol monomethallyl ether based on ethylene glycol used in the reaction was 17.7 mol%.

(Moisture loss process / solid-liquid separation process)
An oil / water separation tube was attached to the flask after the above reaction, and distillation under reduced pressure was performed with oil / water separation of the distillate under stirring to separate 292.34 g of water. The operation pressure was initially 200 mmHg and later lowered to 100 mmHg, and the dehydration operation was completed when the distillate became a uniform layer.
From the residual slurry after the dehydration operation, the precipitated solid was filtered off using filter paper (No. 5B, 4 μm) to obtain 1709.59 g of filtrate. Further, the solid on the filter paper was washed with 100.22 g (1.61 mol) of ethylene glycol, and the filtrate was obtained by combining 117.64 g of the obtained washing solution and the previous filtrate. At this time, the separated salt was 278.34 g. As a result of gas chromatography analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 80.2 mol%, and the yield of ethylene glycol dimethallyl ether was 11.8 mol% (calculated on the basis of raw material methallyl chloride). . The residual water content was analyzed by the Karl Fischer method and found to be 0.84% by mass.

(Separation process)
1798.28 g of the filtrate obtained in the above step was charged into the bottom of the distillation column to purify ethylene glycol monomethallyl ether. As a distillation facility, distillation was performed under the conditions of a top pressure of 45 mmHg and a bottom temperature of 100 ° C. to 127 ° C. using an apparatus having a tower diameter of 30 mmφ, using regular fillers, and a theoretical plate number of 30 plates. At the beginning of the distillation, the remaining water was concentrated and the tower top condensate was separated into two layers, so that 17.25 g of an aqueous layer was separated by oil-water separation. Thereafter, since the condensate became uniform, distillation was performed at a reflux ratio of 10 to obtain 318.17 g of a distillate containing ethylene glycol monomethallyl ether as a main component. As a result of analysis of the distillate, the water content was 0.06% by mass and the ethylene glycol dimethallyl ether content was 0.47% by mass. In addition, ethylene glycol containing salt as a distillation residue (1289.9 g as a pure component) was recovered.

Example 2
Production of ethylene glycol methallyl ether using ethylene glycol recovered in Example 1 (reaction process)
Ethylene glycol recovered in the distillation step of Example 1 was added to a pure content of 1102.5 g (17.76 mol) and 399.44 g (6.44 mol) of new ethylene glycol. In place of 0.0 g, 490.91 g (NaOH 5.05 mol) of 48 mass% sodium hydroxide solution was charged and heated to 60 ° C. with stirring. Under stirring at 60 ° C., 452.90 g (5.00 mol) of methallyl chloride was added dropwise over 2 hours, followed by reaction at 70 ° C. for 4 hours. The yield of ethylene glycol monomethallyl ether at the end of the reaction was 82.0 mol%. The total yield of ethylene glycol monomethallyl ether based on the total amount of ethylene glycol charged from Example 1 was 25.9 mol%.

(Moisture loss process / solid-liquid separation process)
Dehydration and filtration were carried out in the same manner as in Example 1 except that the operating pressure in the dehydration process was changed to 100 mmHg from the beginning, to obtain 173.34 g of filtrate and 163.14 g of cleaning liquid. The salt separated and recovered at this time was 395.11 g. As a result of analysis, the yield of ethylene glycol monomethallyl ether was 76.8 mol%, and the yield of ethylene glycol dimethallyl ether was 13.4 mol% (calculated on the basis of raw material methallyl chloride). Moreover, the residual water content was 1.16 mass%.

(Separation process)
Using the same distillation equipment as in Example 1, 1839.60 g of the reaction liquid and washing liquid recovered in the previous step were charged into the bottom of the distillation tower to purify ethylene glycol monomethallyl ether. At the beginning of distillation, 24.30 g of the aqueous layer was separated by oil-water separation of the refluxed liquid separated into two layers. Then, after the reflux rate was extracted at 20 with the distillation rate up to 3.2% as the initial fraction, the reflux ratio was changed to 10 and the main fraction was withdrawn. When the distillation rate reached 15.7% by mass, (i) total reflux for 15 minutes and (ii) 3.3 g of the liquid in the reflux tank was extracted in a short time, and the operation consisting of 38 times was repeated. Thereafter, a distillation rate of 23.6% to 32.8% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing salt (1083.69 g as a pure component) was recovered as a distillation residue. By the distillation operation, 375.40 g of a fraction containing ethylene glycol monomethallyl ether as a main component was obtained. As a result of analysis, the water content was 0.06% by mass, and the ethylene glycol dimethallyl ether content was 0.29% by mass.

Comparative Example (Production Example in which the molar ratio of alkylene glycol to unsaturated halogen compound is 1)
A 2 L flask was charged with 310.35 g (5.00 mol) of ethylene glycol, 420.83 g (NaOH 5.05 mol) of a 48 mass% aqueous sodium hydroxide solution, and 459.64 g (5.00 mol) of methallyl chloride, and the same as in Example 1. The reaction was carried out. As a result of analysis, the yield of ethylene glycol monomethallyl ether at the end of the reaction was 24.6 mol%, and the yield of ethylene glycol dimethallyl ether was 26.8 mol% (calculated on the basis of raw material methallyl chloride).

Example 3
(First reaction process / moisture reduction process)
A 2 L flask was charged with 150.96 g (24.20 mol) of ethylene glycol and 205.08 g (5.05 mol) of flake sodium hydroxide, and the reaction was carried out while changing the temperature from room temperature to 125 ° C. at a pressure of 20 mmHg. . At the same time, water was distilled by simple distillation to recover 131.31 g of the fraction.

(Second reaction step)
While stirring, 452.80 g (5.00 mol) of methallyl chloride was dropped over 3 hours at 65 to 70 ° C. under normal pressure to the moisture-reducing composition liquid obtained in the above step, and then reacted at 70 ° C. for 6 hours. 2014.11g of reaction mixture containing precipitated salt was obtained.
(Solid-liquid separation process)
The slurry obtained in the previous step was filtered off using filter paper (No. 5B, 4 μm) to obtain 1729.39 g of filtrate. Furthermore, the solid on the filter paper was washed with 100.62 g (1.62 mol) of ethylene glycol, and 121.29 g of the obtained washing liquid was combined with the previous filtrate to obtain a filtrate. The salt separated and recovered at this time was 259.53 g. As a result of gas chromatography analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 83.3 mol%, and the yield of ethylene glycol dimethallyl ether was 12.2 mol% (calculated on the basis of raw material methallyl chloride). . Further, when the residual water content was analyzed by the Karl Fischer method, it was 0.10% by mass.
(Separation process)
Using the same distillation equipment as in Example 1, 1728.00 g of the reaction solution and the washing solution recovered in the previous step were charged into the bottom of the distillation column to purify ethylene glycol monomethallyl ether. At the beginning of distillation, 5.68 g of water concentrate was collected from the reflux tank. Then, after the reflux ratio was extracted at 20 with the distillation rate up to 1.3% as the initial fraction, the reflux ratio was changed to 10 and the main fraction was extracted. Thereafter, the distillation rate from 23.2% to 29.1% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing salt (1153.31 g as a pure component) was recovered as a distillation residue. By the distillation operation, a fraction containing 378.63 g of ethylene glycol monomethallyl ether as a main component was obtained. As a result of analysis, the water content was 0.09% by mass, and the ethylene glycol dimethallyl ether content was 0.36% by mass.
Example 4
The ethylene glycol used in the first reaction step was 1489.71 g (24.00 mol), the flake sodium hydroxide was 123.20 g (3.03 mol), and 271.77 g (3.00 mol) methallyl chloride used in the second reaction step. The experiment was conducted in the same manner as in Example 4 except that. The filtrate, washing solution and salt obtained in the solid-liquid separation step were 1648.76 g, 123.84 g and 101.10 g, respectively. When the filtrate was analyzed, the yield of ethylene glycol monomethallyl ether was 89.0 mol%, and the yield of ethylene glycol dimethallyl ether was 7.2 mol% (calculated on the basis of raw material methallyl chloride). The residual water content was 0.10% by mass.

  As described above, it is shown that an unsaturated ether composition can be obtained in a high yield by reacting the polyhydric alcohol (1) and the unsaturated halogen compound at a preferable ratio. Furthermore, the polyhydric alcohol (1) It was found that an unsaturated ether composition was efficiently produced by carrying out the reaction using a recovered composition containing. Moreover, it became clear that the unsaturated ether composition can be produced efficiently by the steps shown in Method A and Method B.

Claims (10)

Polyhydric alcohol represented by the following general formula (1) and HO— (A—O—) n—H (1)
(In formula, n represents the number of 1-4. A is a C2-C18 alkylene group which may have a substituent, and a substituent represents an alkyl group and a hydroxyl group.)
Unsaturated halogen compound represented by the following general formula (2) and RX (2)
(In the formula, R represents an alkenyl group, and X represents a halogen.)
In the method for producing an unsaturated ether composition comprising at least one unsaturated ether compound having a hydroxyl group, using an alkali metal and / or alkaline earth metal inorganic compound (IN) exhibiting basicity, The manufacturing method of the unsaturated ether composition characterized by using the said polyhydric alcohol (1) 1.5 mol or more with respect to 1 mol of unsaturated halogen compounds (2). The unsaturated ether composition comprises a monounsaturated ether (M) having one unsaturated ether group and a diunsaturated ether (D) having two unsaturated ether groups, (M) The method for producing an unsaturated ether composition according to claim 1, wherein (D) is a mass ratio of 0.01 to 25 parts by mass with respect to 100 parts by mass. The method for producing an unsaturated ether composition according to claim 1 or 2, wherein the unreacted polyhydric alcohol (1) is recovered and reused at least in part as a raw material. The method for producing an unsaturated ether composition according to claim 1, further comprising a step of removing the precipitated alkali metal and / or alkaline earth metal halide. The method for producing an unsaturated ether composition according to claim 1, wherein the unsaturated halogen compound is one or two selected from (meth) allyl chloride and / or (meth) allyl bromide. The method for producing an unsaturated glycol ether composition according to claim 1, wherein the polyhydric alcohol (1) is a (poly) alkylene glycol. The method for producing an unsaturated ether composition according to claim 1, wherein the inorganic compound (IN) is an alkali metal hydroxide. The method for producing an unsaturated ether composition according to claims 1 to 7, comprising the steps a) to f) described below: a) the inorganic compound (IN) and the polyhydric alcohol (1) And / or a first reaction step using a recovered composition from the following recovery step b) a moisture reduction step c) obtained at the same time as the first reaction step and / or after completion of the first reaction step c) obtained in the moisture reduction step A second reaction step in which the obtained low water content composition and the unsaturated halogen compound (2) are reacted. D) The reaction composition obtained in the second reaction step is treated with a halogen of an alkali metal and / or an alkaline earth metal. A solid-liquid separation step for separating a solid precipitate containing a compound and a solution containing an unsaturated ether compound; e) from the solution containing the unsaturated ether compound obtained in the solid-liquid separation step, Recovery step using a portion or all of the resulting collection composition separation step f) the separation step of separating into a collection composition comprising an alcohol to the first reaction step A method for producing an unsaturated ether composition according to claims 1 to 7, characterized by comprising the following steps g) to k): g) the inorganic compound (IN) and the polyhydric alcohol (1) And / or reaction step h to obtain a reaction composition containing an unsaturated ether composition using the recovered composition from the following recovery step and the unsaturated halogen compound (2) h) reaction composition obtained in the reaction step Moisture reduction step of obtaining a low water content composition by reducing the water content from the product i) Solid precipitate containing an alkali metal and / or alkaline earth metal halide and an unsaturated ether compound The solid-liquid separation step j) is separated from the solution containing the unsaturated ether compound obtained in the solid-liquid separation step into the recovered composition containing the unsaturated ether composition and the polyhydric alcohol. Recovery step using a portion or all of the resulting collection composition separation step k) said separation step of releasing the reaction step The unsaturated ether composition obtained by the manufacturing method of Claims 1-9