KR101006007B1 - Method of manufacturing polyoxy alkylene alkenyl ether using heterogeneous base - Google Patents

Abstract

The present invention provides a method for preparing a polyoxy alkylene alkenyl ether by reacting a heterogeneous base, a polyoxy alkylene alcohol, and an alkenyl halide on a non-aqueous solvent. Is a process for producing a polyoxy alkylene alkenyl ether, characterized in that it can form a homogeneous mixture with the polyoxy alkylene alkenyl ether as a reaction product; And to polyoxy alkylene alkenyl ethers prepared by the above process.

The present invention also relates to a process for preparing polyoxy alkylene alkenyl ethers in which the reaction by-products become heterogeneous salts in the non-aqueous solvent, thereby facilitating removal of the reaction by-products.

Polyoxy alkylene alkenyl ethers, non-aqueous solvents, heterogeneous bases.

Description

Method for preparing polyoxyalkylene alkenyl ether using heterogeneous base {METHOD OF MANUFACTURING POLYOXY ALKYLENE ALKENYL ETHER USING HETEROGENEOUS BASE}

1 is a result of C ¹³ -NMR analysis of the MPEG allyl ether prepared in Example 1. FIG.

2 is a result of H-NMR analysis of the MPEG allyl ether prepared in Example 1.

3 is a C ¹³ -NMR analysis result of the MPEG allyl ether prepared in Comparative Example 1.

4 is an H-NMR analysis result of the MPEG allyl ether prepared in Comparative Example 1 .

The present invention relates to a process for preparing polyoxy alkylene alkenyl ethers that facilitates the removal of reaction byproducts.

Polyoxy alkylene alkenyl ether is one of polyoxy alkylene alcohol derivatives and is generally used as a raw material for dispersing agents, fluidizing agents, surfactants, coating agents or coatings, and also includes polymerizable double bonds. It is widely used as a polymer for addition reaction with a polymerizable monomer or a silicon SiH.

The polyoxy alkylene alkenyl ether is usually prepared through the addition reaction of alkenyl alcohol and alkylene oxide such as ethylene oxide or propylene oxide under high temperature and high pressure. However, it is difficult to equip the equipment capable of withstanding high temperature and high pressure and the addition technology of alkyl oxide, and the polyoxy alkylene alkenyl ether prepared by the above method has a hydroxyl group at the terminal, so that it functions as a functional group in the subsequent polymerization. May cause side reactions.

In order to solve the above-mentioned problems, a method for producing polyoxy alkylene alkenyl ether through substitution reaction of alkenyl chloride and polyoxy alkylene alcohol without using alkenyl alcohol has been proposed, but under high temperature and high pressure conditions It did not solve the problem of performing a substitution reaction.

On the other hand, a method of preparing polyoxy alkylene alkenyl ether by using a substitution reaction of an organic base and alkenyl halide and polyoxy alkylene alcohol in a general organic solvent has been proposed, but it is impossible to separate organic salts, which are by-products, as a raw material. There is a disadvantage that cannot be used.

In addition, a method of preparing a polyoxyalkylene alkenyl ether at high temperature by reacting an alkenyl halide and a polyoxy alkylene alcohol under an alkali metal compound, and adding water to remove an inorganic salt as a byproduct has been proposed (Japanese Patent) No. 3005629). However, since the polyoxyalkylene alkenyl ether contains oxygen atoms repeatedly in the carbon skeleton (see Formula 1 below), the polyoxyalkylene alkenyl ether has affinity for water as well as non-aqueous substances such as organic solvents. Water may be included on the oxy alkylene alkenyl ether. As described above, the water contained in the polyoxyalkylene alkenyl ether causes problems in the reaction of the SiH of the silicon and the polyoxy alkylene alkenyl ether, such as the performance, yield and purity of the polyoxy alkylene alkenyl ether. It may affect the back.

[Formula 1] R ₁ O (AO) _n R ₂

In Formula 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, R ₂ is an alkenyl group having 1 to 10 carbon atoms, n is 2 to 200, and AO is at least one C ₁ to C ₆ alkoxy group.

In the present invention, when the multicomponent mixture is a heterogeneous mixture, it is possible to separate each component through a relatively simple process such as filtration, thereby producing a reaction when preparing a polyoxyalkylene alkenyl ether. By allowing the mixture to form a heterogeneous mixture of a first phase comprising a polyoxy alkylene alkenyl ether and a second phase comprising a reaction byproduct, polyoxy facilitates separation of the reaction byproduct. It is intended to provide a process for the preparation of alkylene alkenyl ethers.

The present invention provides a method for preparing a polyoxy alkylene alkenyl ether by reacting a heterogeneous base, a polyoxy alkylene alcohol, and an alkenyl halide on a non-aqueous solvent. Is a process for producing a polyoxy alkylene alkenyl ether, characterized in that it can form a homogeneous mixture with the polyoxy alkylene alkenyl ether as a reaction product; And polyoxy alkylene alkenyl ethers prepared by the above process.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Method for producing a polyoxy alkylene alkenyl ether according to the present invention comprises a non-aqueous solvent capable of forming a homogeneous mixture with the reaction product polyoxy alkylene alkenyl ether; And introducing a base capable of producing a heterogeneous salt on the non-aqueous solvent, thereby allowing the salt of the reaction by-product to be present in the heterogeneous phase on the non-aqueous solvent to remove the salt of the reaction by-product. It is characterized by facilitating the.

The non-aqueous solvent used in the present invention may be any non-aqueous solvent having high solubility in the reaction product polyoxy alkylene alkenyl ether, which can form a homogeneous mixture with the polyoxy alkylene alkenyl ether. Can be used. Non-limiting examples of such non-aqueous solvents include polar organic solvents such as methylene chloride, acetonitrile, ethyl acetate, methylethyl ketone, chloroform, chlorobenzene, dimethyl acetamide, dimethylformamide, dimethyl sulfoxide and pentane, hexane, heptane And nonpolar organic solvents such as diethyl ether, toluene, benzene, xylene, cyclohexane, cyclopentane, carbon tetra chloride, tetrahydrofuran, and these non-aqueous solvents may be used alone or in combination of two or more thereof. Can be.

In addition, the base used as the reaction material in the present invention is not particularly limited so long as it is a base having a low solubility in the non-aqueous solvent and can form a heterogeneous phase in the non-aqueous solvent. It is preferable to use 10 weight part or more and 100 weight part or less per 100 weight part of len alcohol. Examples of the base include sodium hydroxide, calcium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxylated, potassium methoxylated, lithium methoxylated, sodium ethoxylated, calcium ethoxylated, lithium ethoxylated, potassium ethoxylated, and the like. . These bases can be used individually or in mixture of 2 or more types.

On the other hand, in the method for preparing a polyoxyalkylene alkenyl ether according to the present invention, a heterogeneous salt may be generated as a reaction byproduct on the non-aqueous solvent used by using the base and the alkenyl halide as the reaction material. The reaction byproduct salt may comprise a cation derived from the base and a halogen anion derived from the alkenyl halogen and used from the nature of the base to form a heterogeneous phase in a non-aqueous solvent. It may be present in a heterogeneous system on a non-aqueous solvent.

The above-described solubility characteristics of the non-aqueous solvent and base used in the present invention; And, due to the heterogeneous nature of the non-aqueous solvent of the salt as a reaction byproduct, in the preparation of the polyoxy alkylene alkenyl ether, the reaction product mixture comprises a first phase comprising a non-aqueous solvent and the final product, polyoxy alkylene alkenyl ether. It is possible to form a heterogeneous system composed of a second phase containing a salt which is heterogeneous in the above-mentioned non-aqueous solvent phase as a reaction by-product. As a result, the present invention can easily remove the salt of the reaction by-product from the reaction mixture by removing the second phase.

More specifically, the present invention can remove the salts of the reaction by-products with only a simple process of filtration of the reaction product mixture without additional introduction of water or other compounds to remove salts of the reaction by-products. Thus, in the process for preparing polyoxy alkylene alkenyl ethers, when water or another compound is introduced to remove salts that are reaction by-products from the reaction product mixture, the final product polyoxy alkylene alkenyl ethers contain water or The polyoxy alkylene alkenyl ether may cause side reactions with the compound introduced above, which may cause the performance, yield, and purity of the polyoxy alkylene alkenyl ether to be lowered. Such a problem is less likely to occur, and furthermore, high purity polyoxy alkylene alkenyl ether can be obtained.

The present invention uses a polyoxy alkylene alcohol, alkenyl halide in addition to the base as a reaction material.

The polyoxy alkylene alcohol may be represented by the following Formula 2, it may be used in an amount of 10 to 100 parts by weight per 100 parts by weight of the non-aqueous solvent.

Formula ₁ R ₁ O (AO) _n H

In Formula 1, R 1 is an alkyl group having 1 to 12 carbon atoms, n is 2 to 200, and AO is one or more C ₁ to C ₆ alkoxy groups.

In addition, the alkenyl halide may be represented by the following formula (3), 10 parts by weight or more per 100 parts by weight of the polyoxy alkylene alcohol, preferably 10 parts by weight or more per 100 parts by weight of polyoxy alkylene alcohol 100 parts by weight It can be used as follows. The amount of the alkenyl halide is high in the equivalence ratio of alkenyl halide to polyoxy alkylene alcohol, so that all polyoxy alkylene alcohol can be consumed in the reaction, and thus the boiling point is very high and can not be easily removed by distillation. Removal of oxy alkylene alcohol may be unnecessary.

(3)

In Formula 3, R ₃ is hydrogen, methyl group (CH ₃ ) or ethyl group (C ₂ H ₅ ), k is 1 to 6, and X is halogen.

The present invention can be carried out at 0 to 40 ℃ and under normal pressure by the introduction of the non-aqueous solvent and the base. As described above, the non-aqueous solvent acts as an element for easy removal of salts, which are reaction by-products, and at the same time, disperses the reactants to improve the contact force between the reactants and effectively removes the heat generated during the reaction. It is possible to make the reaction to produce polyoxy alkylene alkenyl ethers even at 0 to 40 ° C. and atmospheric pressure. This allows the present invention to produce polyoxy alkylene alkenyl ethers at low cost and high efficiency.

The present invention can easily remove salts and excess reactants (eg, bases), which are reaction by-products, by simultaneously or sequentially introducing non-aqueous bases, polyoxy alkylene alcohols, and alkenyl halides in the non-aqueous solvents. It is possible to produce a high purity polyoxy alkylene alkenyl ether, more preferred examples are as follows.

The present invention comprises the steps of: i) introducing 10 to 100 parts by weight of polyoxy alkylene alcohol to 100 parts by weight of a non-aqueous solvent; Ii) introducing at least 10 parts by weight of a heterogeneous base and an alkenyl halide on the non-aqueous solvent into each mixture in step iii) per 100 parts by weight of the polyoxy alkylene alcohol; V) stirring the mixture of step ii) at 0-40 ° C. and atmospheric pressure to carry out the reaction; Iii) filtering the reaction mixture in step iii) to remove salts as reaction by-products and bases as excess reactants; And iii) removing the alkenyl halide, which is a non-aqueous solvent and a surplus reactant, by distilling the filtrate under reduced pressure.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One

To 100 parts by weight of methylene chloride was added 100 parts by weight of MPEG (polyoxy alkylene alcohol containing 13 ethoxy, concentrated) and 11 parts by weight of sodium hydroxide with constant stirring. 10 parts by weight of allyl chloride was added using a dropping funnel, and the mixture was allowed to react for 12 hours while stirring at room temperature (RT) and atmospheric pressure. Thereafter, a filter was removed to remove residual sodium hydroxide and salts of the reaction by-products, and the remaining mixture was heated to 80 ° C. and distilled under reduced pressure for 3 hours to remove residual allyl chloride and organic solvent to remove polyoxy alkylene alkenyl. Ether was prepared.

Example 2

A polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 1, except that 16.5 parts by weight and 15 parts by weight of sodium hydroxide and allyl chloride were used instead of 11 parts by weight and 10 parts by weight, respectively.

Example  3

A polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 1, except that 22 parts by weight and 10 parts by weight of sodium hydroxide and allyl chloride were used instead of 11 parts by weight and 10 parts by weight, respectively.

Example  4

A polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 1, except that 22 parts by weight and 20 parts by weight of sodium hydroxide and allyl chloride were used instead of 11 parts by weight and 10 parts by weight, respectively.

Example  5

The polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 1, except that 33 parts by weight and 30 parts by weight of sodium hydroxide and allyl chloride were used instead of 11 parts by weight and 10 parts by weight, respectively.

Example  6

A polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 2, except that acetonitrile was used instead of methylene chloride.

Example  7

Polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 6, except that the reaction was carried out for 2 hours instead of 12 hours.

Example 8

A polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 6, except that the reaction was performed for 4 hours instead of 12 hours.

Example  9

A polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 6, except that the reaction was carried out for 6 hours instead of 12 hours.

Example 10

Instead of 13 moles of MPEG, MPEG 8 moles (polyoxy alkylene alcohol containing 8 ethoxys) are used, and 11 parts by weight, 25 parts by weight, and 22 parts by weight instead of 10 parts by weight of sodium hydroxide and allyl chloride are respectively used. A polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 1 except that it was used.

Example  11

Instead of 13 moles of MPEG, MPEG 23 moles (polyoxy alkylene alcohols containing 23 ethoxy) were used, and 11 parts by weight and 10 parts by weight instead of 10 parts by weight and 9 parts by weight of sodium hydroxide and allyl chloride were used, respectively. Polyoxyalkylene alkenyl ether was prepared in the same manner as in Example 1, except that the reaction was performed for 6 hours instead of 12 hours.

Comparative Example 1

100 parts by weight of MPEG 13 mol (polyoxy alkylene alcohol containing 13 ethoxy, concentrated) 100 parts by weight was added to 100 parts by weight of pyridine serving as a non-aqueous solvent and a base while stirring. 10 parts by weight of allyl chloride was added using a dropping funnel, and the reaction was performed for 12 hours while stirring the mixture at room temperature (RT) and atmospheric pressure. The remaining mixture was heated to 80 ° C. and distilled under reduced pressure for 3 hours to remove residual allyl chloride and residual pyridine solvent.

Experimental Example

Table 1 shows the conversion rates for the polyoxyalkylene alkenyl ethers prepared in Examples 1 to 11 and Comparative Example 1. In this case, the conversion rate is a value analyzed by LC (Liquid Chromatography).

Since the polyoxy alkylene alkenyl ethers of Examples 1 to 11 and Comparative Example 1 were purified through distillation under reduced pressure, and no loss occurred during the separation process, the yield was represented by the same value as the conversion rate.

On the other hand, as a result of NMR analysis, in Examples 1 to 11, no substances other than polyoxy alkylene alkenyl ether were detected, and their purity was represented by the same value as the conversion rate, but in Comparative Example 1, polyoxy alkylene al In addition to the kenyl ether, the reaction by-product pyridine salt was detected, the purity thereof was calculated by the molecular weight.

TABLE 1

division Polyoxy Alkylene
Alcohol base
usage
( Parts by weight ) Allyl chloride
( Parts by weight ) menstruum Reaction time
( hour ) % Conversion Yield (%) Purity (%) Kinds
( EO
confiscation) usage
(Parts by weight) Example 1 13 100 11 10 CH ₂ Cl ₂ 12 50 50 50 Example 2 13 100 16.5 15 CH ₂ Cl ₂ 12 72 72 72 Example 3 13 100 22 10 CH ₂ Cl ₂ 12 80 80 80 Example 4 13 100 22 20 CH ₂ Cl ₂ 12 83 83 83 Example 5 13 100 33 30 CH ₂ Cl ₂ 12 100 100 100 Example 6 13 100 16.5 15 CH ₃ CN 12 100 100 100 Example 7 13 100 16.5 15 CH ₃ CN 2 65 65 65 Example 8 13 100 16.5 15 CH ₃ CN 4 74 74 74 Example 9 13 100 16.5 15 CH ₃ CN 6 100 100 100 Example 10 8 100 25 22 CH ₃ CN 6 100 100 100 Example 11 23 100 10 9 CH ₃ CN 6 100 100 100 Comparative Example 1 13 100 100 10 - 12 100 100 84.7

As a result of comparing the Examples and Comparative Examples with the same conversion and yield in Table 1, polyoxyalkylene alkenyl ethers were prepared using a non-uniform base in a non-aqueous solvent according to the present invention (Examples 1 to 11). The polyoxyalkylene alkenyl ether was prepared using a homogeneous base on a non-aqueous solvent (comparative example 1), showing much higher purity. When polyoxyalkylene alkenyl ether is prepared using a heterogeneous base on a non-aqueous solvent according to the present invention (Examples 1 to 11), a non-uniform salt is produced as a reaction by-product on the non-aqueous solution. Since the removal thereof is very easy, it was found that a high purity polyoxyalkylene alkenyl ether can be prepared.

The present invention can easily remove salts of reaction by-products with a simple process of filtration of the reaction product mixture without additional introduction of water or compounds to remove salts of reaction by-products. In addition, there is little possibility that the performance, yield, purity, etc. of the polyoxy alkylene alkenyl ether are reduced by the process for removing the reaction by-products, and further, high purity polyoxy alkylene alkenyl ether can be obtained.

In addition, the present invention can produce a polyoxy alkylene alkenyl ether at 0 to 40 ℃ and under normal pressure, it is possible to produce a polyoxy alkylene alkenyl ether at low cost, it is possible to improve the economics and efficiency.

Various modifications may be made without departing from the spirit and scope of the invention as set forth in the claims.

Claims (8)

A method for preparing a polyoxy alkylene alkenyl ether by reacting a heterogeneous base, a polyoxy alkylene alcohol, and an alkenyl halide on a non-aqueous solvent, wherein the non-aqueous solvent is a reaction product. Form a homogeneous mixture with phosphorus polyoxy alkylene alkenyl ether, In preparing the polyoxy alkylene alkenyl ethers, the reaction product mixture comprises a first phase comprising a non-aqueous solvent and a polyoxy alkylene alkenyl ether; And a reaction by-product comprising a cation derived from a polyoxy alkylene alcohol and a halogen anion derived from an alkenyl halide, characterized in that it is a heterogeneous mixture composed of a second phase comprising a heterogeneous salt in said non-aqueous solvent. Process for preparing phosphorus polyoxy alkylene alkenyl ether. According to claim 1, wherein the production method is characterized in that carried out at 0 to 40 ℃ and under normal pressure. delete The method of claim 1, further comprising removing the second phase. 5. The method of claim 4, wherein said removing step is by filtration. The method of claim 1, wherein the non-aqueous solvent is methylene chloride, acetonitrile, ethyl acetate, methyl ethyl ketone, chloroform, chlorobenzene, dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, pentane, hexane, heptane, diethyl A process selected from the group consisting of ether, toluene, benzene, xylene, cyclohexane, cyclopentane, carbon tetra chloride and tetrahydrofuran. The method of claim 1, wherein the base is composed of sodium hydroxide, calcium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxylated, potassium methoxylated, lithium methoxylated, sodium ethoxylated, calcium ethoxylated, lithium ethoxylated and potassium ethoxylated Manufacturing method characterized in that selected from the group. delete

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