JP2010241772A - Method for producing unsaturated polyalkylene glycol ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially simply producing a high quality unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain. <P>SOLUTION: This method for producing the unsaturated (poly)alkylene glycol ether (C) by reacting a halogenated compound (A) having an unsaturated bond with a polyhydric alcohol is provided by performing the reaction of the halogenated compound (A) having the unsaturated bond with the polyhydric alcohol (B) by using at least one kind of a substance (M) selected from an alkali metal, alkaline earth metal, alkali metal hydride and alkaline earth metal hydride. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing an unsaturated polyalkylene glycol ether having a polyalkylene oxide chain that can be suitably used as a raw material for a polycarboxylic acid polymer that can be used in cement compositions such as cement paste, mortar, and concrete. .

  The unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain is a useful compound as a copolymerization component of a polycarboxylic acid polymer used in a cement composition.

  As a method for producing an unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain, a halide (A) having an unsaturated bond and a polyhydric alcohol (B) are converted into an alkali compound (alkali (earth) metal water). An unsaturated (poly) alkylene glycol ether (C) by reacting with an oxide, an alkali (earth) metal carbonate, etc., and then the resulting unsaturated (poly) alkylene glycol ether (C) Discloses a method for producing an unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain by adding an alkylene oxide (D) to (see Patent Document 1).

  When the alkylene oxide (D) is added to the unsaturated (poly) alkylene glycol ether (C) obtained by the disclosed method, the water content in the unsaturated (poly) alkylene glycol ether (C) is reduced to a specific ratio or less. It has been found that purification is important. In the process of studying an industrial manufacturing process, the inventors of the present application have found a device that can further reduce the amount of water and can simplify the manufacturing process, and have completed the present invention.

  Also, an alkali metal alcoholate of a polyoxyalkylene compound obtained by reacting a polyoxyalkylene compound with an alkali metal or an alkali metal compound (metal sodium, potassium hydroxide, sodium hydroxide, sodium methylate, etc.) and an organic halide. A method for producing an organic (poly) alkylene glycol ether by reaction is disclosed (see Patent Document 2). This document does not disclose the necessity of reducing the amount of water, but conversely describes a purification method by adding water. In the examples, only alkali metal hydroxides are described.

Japanese Patent Application Laid-Open No. 2008-274258 Japanese Patent Application Laid-Open No. 60-4530

  An object of the present invention is to provide a method for efficiently producing an unsaturated (poly) alkylene glycol ether (C) while keeping the water content extremely low. Further, when the alkylene oxide (D) is added to the unsaturated (poly) alkylene glycol ether (C), if water remains in the unsaturated (poly) alkylene glycol ether (C), the addition reaction can be obtained. In order to solve the problem that the purity of the unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain is lowered and the performance is lowered when used as a copolymer component of a polycarboxylic acid polymer. An object is to provide a devised manufacturing method.

Means for solving the problems include the following.

  (1) A method for producing an unsaturated (poly) alkylene glycol ether (C) by reacting a halide (A) having an unsaturated bond with a polyhydric alcohol (B), the halogen having an unsaturated bond The compound (A) and the polyhydric alcohol (B) are reacted using at least one substance (M) selected from alkali metals, alkaline earth metals, alkali metal hydrides, and alkaline earth metal hydrides. A method for producing an unsaturated (poly) alkylene glycol ether (C),

  (2) Unsaturation (characterized by using the substance (M) in a range in which the total metal valence is 0.5 to 2.0 mol with respect to 1 mol of the unsaturated halogen compound (A)). Production method of poly) alkylene glycol ether (C).

  (3) The unsaturated (poly) alkylene glycol ether described above, wherein the polyhydric alcohol (B) is used in an amount of 1.5 to 10 mol with respect to 1 mol of the unsaturated halogen compound (A). C) Production method.

(4) A process for producing the unsaturated (poly) alkylene glycol ether (C), which comprises the following steps a) to d).
a) First reaction step for reacting the substance (M) with the polyhydric alcohol (B) b) Second reaction for reacting the reaction composition obtained in the first reaction step with the unsaturated halogen compound (A) Reaction step c) The reaction composition obtained in the second reaction step is a solution containing a solid precipitate containing an alkali metal and / or alkaline earth metal halide and an unsaturated (poly) alkylene glycol ether (C). A solid-liquid separation step in which the unsaturated (poly) alkylene glycol ether (C) and the polyhydric alcohol are obtained from the solution containing the unsaturated (poly) alkylene glycol ether (C) obtained in the solid-liquid separation step. The refinement | purification separation process isolate | separated into the collection composition containing (B).

(5) The unsaturated (poly) alkylene glycol described above, further comprising e) a recovery step in which a part or all of the recovered composition obtained in the purification and separation step is used in the first reaction step. A method for producing ether (C).

  (6) The unsaturated (poly) alkylene glycol ether (C) obtained by the method described in the above (1) to (5) is used, and an alkylene oxide (D) is added thereto. A method for producing an unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain.

According to the present invention, high-quality unsaturated (poly) alkylene glycol ether (C) and unsaturated polyalkylene glycol ether (E) can be easily produced industrially.

  The present invention relates to a method for producing an unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain by adding an alkylene oxide (D) to an unsaturated (poly) alkylene glycol ether (C). Poly) alkylene glycol ether (C) is obtained by converting halide (A) and polyhydric alcohol (B) having an unsaturated bond from alkali metal, alkaline earth metal, alkane metal hydride, and alkaline earth metal hydride. An unsaturated polyalkylene glycol ether having a polyalkylene oxide chain (C), which is an unsaturated (poly) alkylene glycol ether (C) obtained by performing a reaction using at least one substance (M) selected E) production method.

In the production of the unsaturated (poly) alkylene glycol ether (C), it can be more efficiently produced by having the following steps a) to e).
a) First reaction step for reacting the substance (M) with the polyhydric alcohol (B) b) Second reaction for reacting the reaction composition obtained in the first reaction step with the unsaturated halogen compound (A) Reaction step c) The reaction composition obtained in the second reaction step is a solution containing a solid precipitate containing an alkali metal and / or alkaline earth metal halide and an unsaturated (poly) alkylene glycol ether (C). A solid-liquid separation step in which the unsaturated (poly) alkylene glycol ether (C) and the polyhydric alcohol are obtained from the solution containing the unsaturated (poly) alkylene glycol ether (C) obtained in the solid-liquid separation step. (B) A purification / separation step for separating the recovered composition e) A recovery step in which part or all of the recovery composition obtained in the purification / separation step is used in the first reaction step.

<Halide having an unsaturated bond (A)>
The halide having an unsaturated bond is preferably a halide having an alkenyl group having 2 to 6 carbon atoms. The alkenyl group is more preferably an alkenyl group having 3 to 5 carbon atoms, still more preferably an alkenyl group having 3 to 4 carbon atoms, and particularly preferably an alkenyl group having 4 carbon atoms.

  Specific examples of the alkenyl group include 3-methyl-3-butenyl, 4-pentenyl, 3-pentenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, and the like. An alkenyl group having 5 carbon atoms; an alkenyl group having 4 carbon atoms such as a methallyl group, 3-butenyl group, 2-butenyl, 1-methyl-2-propenyl; an alkenyl group having 3 carbon atoms such as a propenyl group or an isopropenyl group Is preferred. Among these, 3-methyl-3-butenyl, a methallyl group, and an isopropenyl group are more preferable, and a methallyl group is particularly preferable.

  The halogen atom bonded to the alkenyl group is preferably a chlorine atom or a bromine atom. Among these, a chlorine atom is more preferable because it is easily available industrially and has excellent reactivity and handling.

  Specific examples of the halide having an unsaturated bond include one or two of methallyl chloride, 3-methyl-3-butenyl chloride, allyl chloride, 3-butenyl chloride, 4-pentenyl chloride, isopropenyl chloride and the like. More than species are preferred. More preferred are methallyl chloride, 3-methyl-3-butenyl chloride, allyl chloride, and isopropenyl chloride, and more preferred is methallyl chloride.

<Polyhydric alcohol (B)>
The polyhydric alcohol (B) may be an alcohol having two or more hydroxyl groups.
Preferably, the general formula H-O- (A-O-) n-H (B)
(In the formula, n represents a number of 1 to 4. A is an alkylene group having 2 to 18 carbon atoms which may have a substituent, and may be one kind or different from each other. Represents an alkyl group and a hydroxyl group.), (Poly) alkylene glycol having 2 to 18 carbon atoms is preferable, (poly) alkylene glycol having 2 to 8 carbon atoms is more preferable, and carbon number is more preferable. 2-4 (poly) alkylene glycols are 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 (B) can be used as long as it is industrially available, but the purity is preferably 98% by mass or more, more preferably 99% by mass or more, and a polyhydric alcohol with low purity is used. May be used after increasing the purity by a known method such as distillation or treatment with a dehydrating agent.

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

  The amount of the polyhydric alcohol (B) is such that the polyhydric alcohol (B) is 1.5 to 10 mol, preferably 3 to 8 mol, more preferably 1 mol of the unsaturated halogen compound (A). 4 to 6 moles. By controlling the amount of the polyhydric alcohol (B) within the above range, the ratio of the monounsaturated alkylene ether (C) in which one molecule of the unsaturated halogen compound (A) is added to one molecule of the polyhydric alcohol (B). Is preferable because an unsaturated ether having a high molecular weight can be obtained.

  However, if the amount of the polyhydric alcohol (B) is too small, the amount of the diunsaturated ether compound in which two molecules of the unsaturated halogen compound are added to one molecule of the polyhydric alcohol (B) is excessive. The equipment for producing the unsaturated ether composition is undesirably increased, resulting in an increase in production cost.

<Unsaturated (poly) alkylene glycol ether (C)>
The unsaturated (poly) alkylene glycol ether (C) is a compound obtained by reacting a halide having an unsaturated bond with (poly) alkylene glycol.

  When a preferred combination is expressed as (halide having an unsaturated bond, (poly) alkylene glycol), (methallyl chloride, ethylene glycol), (methallyl chloride, diethylene glycol), (methallyl chloride, propylene glycol), (meth) (Yl chloride, dipropylene glycol), (methallyl chloride, ethylene glycol propylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol), (3-methyl-3-butenyl chloride, diethylene glycol), (3 -Methyl-3-butenyl chloride, propylene glycol), (3-methyl-3-butenyl chloride, dipropylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol propylene glycol) Le), and the like (allyl chloride, ethylene glycol), (acrylic chloride, diethylene glycol), (allyl chloride, propylene glycol), (allyl chloride, dipropylene glycol), (allyl chloride, ethylene glycol propylene glycol).

  Among them, (methallyl chloride, ethylene glycol), (methallyl chloride, diethylene glycol), (3-methyl-3-butenyl chloride, ethylene glycol), (3-methyl-3-butenyl chloride, diethylene glycol), (allyl) Chloride, ethylene glycol) and (allyl chloride, diethylene glycol) are preferred.

<Alkylene oxide (D)>
As the alkylene oxide, an alkylene oxide having 2 to 18 carbon atoms is preferable. More preferably, it is a C2-C8 alkylene oxide, More preferably, it is a C2-C4 alkylene oxide.

  Specifically, one or more of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like are preferable, and ethylene oxide is particularly preferable. When adding 2 or more types of alkylene oxide, it is preferable that ethylene oxide is 80 mol% or more. Thereby, it can utilize as a monomer of the polycarboxylic acid-type copolymer which maintains the balance of hydrophilic property and hydrophobicity, and exhibits the outstanding dispersion performance. More preferably, it is 85 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 100 mol%.

<Unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain>
Examples of the unsaturated polyalkylene glycol ether having a polyalkylene oxide chain include an unsaturated (poly) alkylene glycol ether (C) synthesized from the halide (A) having an unsaturated bond and the polyhydric alcohol (B). A compound to which an oxide (D) is added, and examples thereof include (poly) alkylene glycol methallyl ethers. As the average addition mole number of alkylene oxide to (C), a compound obtained by adding 1 to 300 moles is preferable.

<Substance (M)>
The substance (M) used in the present invention is selected from alkali metals, alkaline earth metals, alkali metal hydrides and alkane earth metal hydrides, and may be one kind or two kinds. You may use the above together.

  Examples of the alkali metal include metal lithium, metal sodium, and metal potassium, and examples of the alkaline earth include metal calcium and metal strontium. Examples of the alkali metal hydride include LiH, NaH, and KH, and examples of the alkaline earth metal hydride include CaH 2 and SrH 2. Preferred are metallic lithium, metallic sodium, metallic potassium, LiH, NaH, KH, and CaH2, and more preferred are metallic sodium and NaH.

  The amount of the substance (M) is 0.5 to 2.0 moles, preferably 0.9 to 1.5 moles, based on 1 mole of the unsaturated halogen compound (A). More preferably, it is 1.0-1.2 mol. For example, when the substance (M) is only an alkaline earth metal compound, the molar ratio of the substance (M) to the unsaturated halogen compound (A) is 0.25 to 1.0. , 0, 45 to 0.75, 0.5 to 0.6.

  Below, the manufacturing method of more preferable unsaturated (poly) alkylene glycol ether (C) and unsaturated polyalkylene glycol ether (E) is demonstrated for every process, respectively.

<First reaction step>
A polyalcohol (B) is reacted with at least one substance (M) selected from alkali metals, alkaline earth metals, alkali metal hydrides, and alkaline earth metal hydrides to form metal alcoholates. In this step, it is very important that water is not produced as a by-product, unlike the case of using an alkali metal hydroxide or the like which is a conventional technique.

  If the residual amount of water is large, the amount of polyalkylene glycol produced as a by-product in the later-described alkylene oxide addition step increases, resulting in a decrease in the purity of the unsaturated polyalkylene glycol ether (E) and a decrease in performance. There is a problem. Moreover, since water is by-produced by the reaction in the prior art, it is necessary to cut the water. In that case, the loss of the raw material polyhydric alcohol (B) in the first reaction step becomes large, a purification step described later The problem is that the loss of unsaturated (poly) alkylene glycol ether (C) increases. According to the method of the present invention, these problems can be solved, the unsaturated (poly) alkylene glycol ether (C) can be efficiently produced, and the purity of the unsaturated polyalkylene glycol ether (E) can be improved. I found out that I can.

  In the first reaction step, the raw material may be supplied to the reactor by slowly supplying the substance (M) to the previously charged polyhydric alcohol (B), and conversely, the substance (M). After the whole amount is charged, the polyhydric alcohol (B) may be supplied slowly, or the polyhydric alcohol (B) and the substance (M) may be supplied slowly at the same time. The most preferred form is a method in which all of the polyhydric alcohol is charged and the substance (M) is slowly supplied.

  In this step, an inert solvent may be used, but it is necessary to remove it after the reaction, and the work becomes complicated. In this process, since the heat generated by the reaction is large, it is not preferable to charge both raw materials at once.

  Although the temperature at the time of mixing both raw materials is based also on the kind of polyhydric alcohol (B), -10 degreeC-80 degreeC is preferable, More preferably, it is -10 degreeC-50 degreeC, More preferably, it is -10 degreeC. ~ 30 ° C. It is preferable to control the temperature at the time of mixing to the above range because the polyhydric alcohol (B) does not coagulate. After mixing both raw materials, the temperature is gradually raised and finally the reaction is completed at 40 ° C. or higher, preferably 50 ° C. or higher.

  The reaction pressure in the first reaction step may be any of reduced pressure, normal pressure, and increased pressure. However, since hydrogen is by-produced, it is simple and inexpensive to carry out at normal pressure. There is no particular limitation on the reaction time, and a time during which the conversion rate of the substance (M) is sufficiently high may be set.

  By the above operation, a composition liquid containing an alkali metal or alkaline earth metal alcoholate can be obtained.

<Second reaction step>
In the second reaction step, it is necessary to mix the reaction product obtained in the first reaction step with the halide (A) having an unsaturated bond. In the form of adding the unsaturated halogen compound (A) to the reaction product obtained in the first reaction step, the whole amount may be added at once, or may be added intermittently in multiple portions, You may add continuously over a long time.

  The reaction temperature in the second reaction step varies depending on the types of the polyhydric alcohol (B) and the unsaturated halogen compound (A) and the type and amount of the substance (M), but is usually 40 to 150 ° C. , Preferably it is 50-100 degreeC, More preferably, it is 55-75 degreeC.

  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. Moreover, reaction time is not specifically limited, What is necessary is just to set time for the conversion rate of a raw material unsaturated halogen compound (A) to become high enough under the said reaction conditions.

<Solid-liquid separation process>
The polyvalent alkylene glycol ether (C) having at least one unsaturated ether group and the diunsaturated ether body having two unsaturated ether groups obtained from the previous step and the unreacted polyvalent monomer. A reaction product containing an alcohol (B) and a halide of an inorganic metal is obtained by subjecting a solid precipitate containing an alkali metal and / or alkaline earth metal halide and an unsaturated ether compound to a solid-liquid separation step and a purification separation step. And a recovered composition containing at least unreacted polyhydric alcohol (B).

  The solid-liquid separation method is not particularly limited, and examples thereof include pressure filtration, vacuum filtration, and centrifugation. In addition, when a solid-liquid separation step is provided before the purification separation step, an unsaturated (poly) alkylene glycol ether (C) is contained in the separated solid, so that a polyhydric alcohol (B ) Is preferably used. The use of the recovered composition as a cleaning solvent is particularly preferable because elution of the alkali (earth) 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 purification and separation process described later, and used for the purification and separation process together with the reaction composition, the recovered composition and the like It is used effectively as a reaction raw material in combination or by combining them.

  It is preferable to carry out the step of removing alkali metal and / or alkaline earth metal halide precipitated by solid-liquid separation at least once between the second reaction step and the later-described recovery step. You may divide and implement in multiple times like after a process and after a refining separation process. In the present invention, since the alkali metal and / or alkaline earth metal halide may be dissolved, the solid-liquid separation step is carried out once between the second reaction step and the purification separation step described later. However, this is one of the simple and preferred embodiments.

<Purification and separation process>
The purification / separation step is not particularly limited as long as the target unsaturated (poly) alkylene glycol ether (C) can be separated, such as distillation, crystallization, and extraction.

  As distillation conditions, from the viewpoint of thermal stability of the target unsaturated ether composition containing an unsaturated (poly) alkylene glycol ether (C), the distillation bottom temperature is preferably 160 ° C. or less, more preferably. Is 150 ° C. or lower, more preferably 140 ° C. or lower, and particularly preferably 130 ° C. or lower. The operating pressure is not particularly limited, and a pressure suitable for processing within the above temperature range may be set.

  In the conventional method, in order to increase the purity of the unsaturated (poly) alkylene glycol ether (C) in the step, a low-boiling component having a low concentration, for example, water, is removed, and the reflux column is maintained at the total reflux. It was necessary to devise measures such as removing the low boiling point component by concentrating the low boiling point components in the tank and extracting the liquid in the tank in a short time when the components in the reflux tank were stabilized. On the other hand, according to the present invention, since the amount of residual water in the liquid to be subjected to the separation step is reduced, it is possible to carry out purification without performing a special operation.

<Recovery process>
The recovered composition containing the unreacted polyhydric alcohol (B) obtained in the purification / separation step may be further purified by distillation or the like, but in the practice of the present invention, particularly as purification step, etc. A part or all of the amount can be used as a raw material for the reaction step without performing the above-mentioned treatment, which is simple and highly efficient.

  For example, you may use the polyhydric alcohol (B) containing the dissolved salt obtained as a distillation residue as a raw material of a 1st reaction process as it is. If necessary, polyhydric alcohol (B) may be newly added to the recovered composition, and other recovered compositions, for example, the same kind of unsaturated (poly) alkylene glycol ether (C) may be produced. You may mix with the collection | recovery composition etc. which were obtained from the other manufacturing equipment which is.

<Third reaction step>
A step of producing an unsaturated polyalkylene glycol ether (E) having a polyalkylene oxide chain by adding an alkylene oxide (D) to the unsaturated (poly) alkylene glycol ether (C) (sometimes referred to as a third reaction step). The reaction temperature is preferably in the range of 80 to 170 ° C. More preferably, it is 90-160 degreeC, More preferably, it is 100-150 degreeC. Controlling to the reaction temperature is preferable because it tends to suppress side reactions and increase the yield of the target product.

  In the third reaction step, it is preferable to use a catalyst. Catalysts include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, metal hydrides such as lithium hydride, sodium hydride and potassium hydride, metal lithium, metal sodium and metal Alkali metals such as potassium, alkaline earth metals such as calcium metal, organometallic compounds such as butyl lithium, methyl lithium and phenyl lithium, Lewis acids such as boron trifluoride and titanium tetrachloride, sodium methoxide, potassium methoxide, etc. The metal alkoxides are preferred. More preferred are sodium hydroxide, potassium hydroxide, sodium hydride, metallic sodium and boron trifluoride, and still more preferred are sodium hydroxide, potassium hydroxide, sodium hydride and metallic sodium.

  As the concentration of the catalyst, the mass ratio of the catalyst to the theoretical amount of the target alkylene oxide adduct calculated from the charged raw material is preferably 10,000 ppm or less. More preferably, it is 8000 ppm or less, More preferably, it is 5000 ppm or less, Most preferably, it is 3000 ppm or less.

  In the subsequent reaction, the reaction time is preferably within 50 hours. More preferably, it is within 40 hours, More preferably, it is within 30 hours. By adopting the reaction time, side reactions tend to be suppressed.

  The latter reaction is preferably carried out under pressure. The pressure at the start of the reaction is preferably 0.01 to 0.5 MPa. More preferably, it is 0.05-0.3 MPa, More preferably, it is 0.1-0.2 MPa. The pressure during the addition reaction is preferably 0.9 MPa or less.

  In the latter stage reaction, each raw material may be supplied to the reactor in a batch at an initial stage, or may be sequentially charged. However, a sequential charging method is preferable because the reaction generates heat of reaction.

Hereinafter, an Example is shown and it demonstrates in more detail about the form of this invention. Of course, this invention is not limited to a following example, Various aspects are possible about a detail.
Unless otherwise specified, “%” represents “% by mass”.

  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 device: GC-2014 manufactured by Shimadzu, J & W capillary column DB-1 (0.53 mmφ × 60 m)
Conditions: held at 40 ° C. for 5 min, heated at 10 ° C./min, held at 300 ° 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
(First reaction step)
Into a 3 L flask was charged 1500.3 g (24.17 mol) of ethylene glycol, and the inside was sufficiently purged with nitrogen. While stirring the flask with ice, a total of 116.2 g (5.05 mol) of metallic sodium was slowly added under normal pressure nitrogen atmosphere while stirring, and then the temperature was gradually raised to 70 ° C. A composition liquid containing alcoholate was obtained.

(Second reaction step)
To the reaction composition obtained in the above step, 452.8 g (5.00 mol) of methallyl chloride was dropped over 3 hours at 65 ° C. to 70 ° C. with stirring under normal pressure, and then reacted at 70 ° C. for 6 hours to precipitate. 2035.1 g of reaction mixture containing 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 1741.4 g of filtrate. Furthermore, the solid on the filter paper was washed with 100.3 g (1.62 mol) of ethylene glycol, and 123.7 g of the obtained washing solution was combined with the previous filtrate to obtain a filtrate. The salt separated and recovered at this time was 260.3 g. As a result of gas chromatography analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 84.7 mol%, and the yield of ethylene glycol dimethallyl ether was 13.2 mol% (calculated on the basis of raw material methallyl chloride). . Further, the water content was analyzed by the Karl Fischer method and found to be 0.03% by mass.

(Purification separation process)
A total of 1858.1 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. As a distillation facility, distillation was performed under the conditions of a top pressure of 45 mmHg using a tower diameter of 30 mmφ, a regular packing material, and an apparatus corresponding to 30 theoretical plates. The initial fraction of distillation was 0.8%, and the reflux fraction was withdrawn at 20. The reflux ratio was changed to 10, and the main fraction was withdrawn. Thereafter, the distillation rate of 23.5% to 29.0% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing a salt (1253.0 g as a pure component) was recovered as a distillation residue. By the distillation operation, 421.8 g of a fraction mainly composed of ethylene glycol monomethallyl ether was obtained. As a result of analysis, the water content was 0.04% by mass, and the ethylene glycol dimethallyl ether content was 0.33% by mass.

(Comparative Example 1)
(First reaction process / water loss process)
Into a 3 L flask was charged 1501.3 g (24.2 mol) of ethylene glycol and 205.1 g (5.05 mol) of flake sodium hydroxide, and the reaction was carried out while changing the temperature from room temperature to 125 ° C. with a pressure of 20 mmHg. . At the same time, water was distilled off by simple distillation to collect 195.2 g of fraction (104.7 g of EG).

(Second reaction step)
To the moisture-reducing composition obtained in the above step, 452.8 g (5.00 mol) of methallyl chloride was dropped over 3 hours at 65 ° C. to 70 ° C. with stirring, and then reacted at 70 ° C. for 6 hours. 1956.3 g of a reaction mixture containing a 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 1673.7 g of filtrate. Furthermore, the solid on the filter paper was washed with 100.3 g (1.6 mol) of ethylene glycol, and 120.6 g of the obtained washing solution was combined with the previous filtrate to obtain a filtrate. The salt separated and recovered at this time was 257.0 g. As a result of gas chromatographic analysis of the filtrate, the yield of ethylene glycol monomethallyl ether was 84.4 mol%, and the yield of ethylene glycol dimethallyl ether was 13.1 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 0.07% by mass.

(Purification separation process)
Using the same distillation equipment as in Example 1, 1755.3 g of the reaction liquid and the 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, 6.2 g of a water concentrate was collected from the reflux tank. Then, after the reflux rate was withdrawn at 20 with a distillation rate of up to 1.4% as the initial fraction, the reflux ratio was changed to 10 and the main fraction was withdrawn. Thereafter, a distillation rate of 23.0% to 29.3% was distilled as a high boiling fraction at a reflux ratio of 20, and ethylene glycol containing salt (1157.1 g as a pure component) was recovered as a distillation residue. By the distillation operation, 379.1 g of a fraction mainly composed of ethylene glycol monomethallyl ether was obtained. As a result of analysis, the water content was 0.09% by mass, and the ethylene glycol dimethallyl ether content was 0.38% by mass.

  From the above Examples and Comparative Examples, it was shown that the synthesis of the unsaturated (poly) alkylene glycol ether (C) by the method of the present invention can be efficiently produced with little loss of raw materials and target products. In addition, the unsaturated (poly) alkylene glycol ether (C) obtained by the above examples has a low water content and is suitably used for the production of an unsaturated polyalkylene glycol ether (E) by addition of alkylene oxide (D). I understand that

  The unsaturated polyalkylene glycol ether (E) obtained by the production method of the present invention is a useful compound as a copolymer component of a polycarboxylic acid polymer used in a cement composition.

Claims (5)

A process for producing an unsaturated (poly) alkylene glycol ether (C) by reacting a halide (A) having an unsaturated bond with a polyhydric alcohol (B), the halide (A) having an unsaturated bond (A) ) And polyhydric alcohol (B) using at least one substance (M) selected from alkali metals, alkaline earth metals, alkali metal hydrides, and alkane earth metal hydrides. A method for producing an unsaturated (poly) alkylene glycol ether (C). The said substance (M) is used in the range from which the total of metal valence becomes 0.5-2.0 mol with respect to 1 mol of unsaturated halogen compounds (A), It is characterized by the above-mentioned. A method for producing an unsaturated (poly) alkylene glycol ether (C). The unsaturated (poly) according to claim 1 or 2, wherein the polyhydric alcohol (B) is used in an amount of 1.5 to 10 mol per 1 mol of the unsaturated halogen compound (A). A method for producing alkylene glycol ether (C). The process for producing an unsaturated (poly) alkylene glycol ether (C) according to claims 1 to 3, characterized in that it comprises the following steps a) to d): a) Substance (M) and a polyhydric alcohol (B) first reaction step for reacting b) second reaction step for reacting the reaction composition obtained in the first reaction step with the unsaturated halogen compound (A) c) in the second reaction step Solid-liquid separation step d) for separating the obtained reaction composition into a solid precipitate containing an alkali metal and / or alkaline earth metal halide and a solution containing an unsaturated (poly) alkylene glycol ether (C) A recovery set containing unsaturated (poly) alkylene glycol ether (C) and polyhydric alcohol (B) from the solution containing unsaturated (poly) alkylene glycol ether (C) obtained in the solid-liquid separation step Purification separation step of separating into a thing further,
5. An unsaturated (poly) alkylene glycol ether according to claim 4, further comprising a recovery step in which part or all of the recovered composition obtained in the purification and separation step is used in the first reaction step. C) Production method.