KR101006003B1 - Method of manufacturing polyoxy alkylene alkenyl ether using two-phase reaction - Google Patents

Abstract

The present invention (a) an aqueous solution containing a polyoxy alkylene alcohol and a water-soluble base; And (b) reacting the non-aqueous organic solvent with the non-aqueous solution containing the alkenyl halide to produce a polyoxy alkylene alkenyl ether; And to polyoxy alkylene alkenyl ethers prepared by the above process.

The production method of the present invention can not only prepare the polyoxy alkylene alkenyl ether in high yield by using a non-aqueous organic solvent, but also can be carried out at room temperature and atmospheric pressure, thereby improving economic efficiency and efficiency.

Polyoxy alkylene alkenyl ethers, two-phase reactions, non-aqueous organic solvents, water soluble bases.

Description

METHODS OF MANUFACTURING POLYOXY ALKYLENE ALKENYL ETHER USING TWO-PHASE REACTION}

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.

The present invention (a) an aqueous solution containing a polyoxy alkylene alcohol and a water-soluble base; And (b) reacting a non-aqueous organic solvent with a non-aqueous solution containing an alkenyl halide to produce a polyoxy alkylene alkenyl ether.

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 being widely used as a polymer for addition reaction with a polymerizable monomer or 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 epoxide under high temperature and high pressure. However, this method is difficult to have a control technique capable of adding as many oxy alkylenes as desired to the alkenyl alcohol, and a polyoxy alkylene alkenyl ether having a hydroxy group at the end is prepared to act as a functional group in subsequent polymerization. May cause side reactions.

On the other hand, in the above method, the alkenyl alcohol is added while the ring compound containing oxygen, such as epoxide, is ring-opened, and the ring compound containing oxygen is added and ring-opened to the oxygen of the ring which is ring-opened, thereby producing polyoxyalkylene. As a method for producing the alkenyl ether, it is common to use a cyclic compound having a small molecular weight. However, the above cyclic compounds are mostly gaseous, and the method is carried out through addition and ring opening reactions, and therefore, should be performed under high pressure and high temperature. In addition, at a high temperature, there is a high possibility that a polymer is formed by polymerization of a reaction material having a double bond or a polyoxy alkylene alkenyl ether as a final product. Thus, the method has a problem that the yield of polyoxy alkylene alkenyl ethers usable as polymerizable monomers can be reduced.

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 polyoxyalkylene 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.

The present invention can be used in combination with a non-aqueous solution containing a non-aqueous organic solvent and an aqueous solution containing a water-soluble base to prepare a polyoxy alkylene alkenyl ether in high yield, as well as at 0 to 40 ℃ and atmospheric pressure It is intended to provide a process for preparing polyoxy alkylene alkenyl ethers that is feasible.

The present invention (a) an aqueous solution containing a polyoxy alkylene alcohol and a water-soluble base; And (b) reacting the non-aqueous organic solvent with the non-aqueous solution containing the alkenyl halide to produce a polyoxy alkylene alkenyl ether; And polyoxy alkylene alkenyl ethers prepared by the above process.

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

In the method for preparing polyoxyalkylene alkenyl ether according to the present invention, alkenyl halide, polyoxy alkylene alcohol, and a water-soluble base are used as reaction materials, and a non-aqueous solution and water are introduced by introducing a non-aqueous organic solvent and water. The polyoxyalkylene alkenyl ether can be produced in high yield by carrying out the reaction in an ideal system in solution phase.

In the above ideal system, the aqueous solution phase contains a polyoxy alkylene alcohol and a water-soluble base, and the non-aqueous solution phase contains a non-aqueous organic solvent and an alkenyl halide. The polyoxy alkylene alcohol may spontaneously react with the base to form polyoxy alkylene alkoxide ions. In addition, since the polyoxyalkylene alcohol repeatedly contains an oxygen atom in the carbon skeleton, the oxygen atom and the water molecule may be hydrogen-bonded (see Formula 1 below), so that the polyoxyalkylene alcohol has affinity for water as well as non-aqueous substances such as organic solvents. Amphiphilic substance with

[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 at least one C ₁ to C ₆ alkoxy group.)

By the above-described properties of the polyoxy alkylene alcohol, the polyoxy alkylene alkenyl ether production mechanism of the present invention can be estimated as follows.

[Reaction Mechanism]

The reaction (1) is carried out on an aqueous solution containing polyoxyalkylene alcohol (R-OH) and a water-soluble base (MA), and the polyoxy alkylene alcohol and the water-soluble base react to form a polyoxy alkylene alkoxide ion ( RO ⁻ ) and cations (M ⁺ ) can be produced. In particular, water-soluble base used in the base to be reacted with the polyoxyalkylene alcohol in the present invention include cationic (M ⁺⁾ and negative (A ^-) on the aqueous solution, so the presence in the state of dissociation, a polyoxyalkylene alcohol and the anions ( a ^-) increases the reaction activity between, of (1) reacting a polyoxyalkylene alkoxide ion (RO ^- this direction) is generated can be carried out more actively.

The polyoxyalkylene alkoxide ions (RO ⁻ ) produced in the above (1) reaction generally have amphiphilic properties by carbon chain and ionic properties. Therefore, when the aqueous solution phase and the non-aqueous solution phase are in contact, the polyoxy alkylene alkoxide ions may migrate from the aqueous solution phase to the non-aqueous solution phase (see (2) above).

The polyoxyalkylene alkoxide ions migrated to the non-aqueous solution will react with the alkenyl halides (eg CH ₂ = CH-CH ₂ -X) present in the non-aqueous solution to produce the polyoxy alkylene alkenyl ether. (The reaction (3) above). Meanwhile, a salt (MX) including a halogen anion (X ⁻ ) generated in the reaction (3) and a cation (M ⁺ ) in an aqueous solution may be formed as a reaction byproduct.

In the present invention, the overall reaction for producing the polyoxy alkylene alkenyl ether is carried out by introducing the amphiphilic of the polyoxy alkylene alkoxide ions, the hydrophilic and non-aqueous organic solvents of the halogen anions, and the polyoxy alkylene al. It may proceed in a direction to increase the production of kenyl ether.

Since the polyoxyalkylene alkoxide ions generated in the aqueous solution phase can be amphiphilic and move to the non-aqueous solution phase as described above, according to the Le Chatelier's principle, 1) The reaction may shift equilibrium to produce polyoxyalkylene alkoxide ions.

In addition, since the halogen anions generated in the non-aqueous solution phase have hydrophilicity in view of the nature of the ions, they can move to the aqueous solution phase. Thus, similarly to the above, the reaction (3) of the non-aqueous solution phase may shift the equilibrium toward producing a polyoxy alkylene alkenyl ether.

In addition, the non-aqueous organic solvent introduced in the present invention can smoothly transfer polyoxyalkylene alkoxide ions and halogen anions by clarifying the boundary between the aqueous solution phase and the non-aqueous solution phase. The non-aqueous organic solvent in the non-aqueous solution phase introduced into the reaction corresponding to the water in the aqueous solution phase maintains the ratio of the non-aqueous solution phase to the aqueous solution phase in the ideal system at an appropriate level, and can be contacted with the aqueous solution phase. By increasing the area, the movement between the aqueous and non-aqueous solution phases of the polyoxyalkylene alkoxide ions and the halogen anions can be facilitated. This increases the degree of equilibrium shift of the reactions (1) and (3), thereby increasing the yield of the polyoxy alkylene alkenyl ether.

[Schematic diagram of reaction equilibrium shift]

On the other hand, the present invention can be carried out at room temperature (0 to 40 ℃) and under normal pressure by introducing a non-aqueous organic solvent and a water-soluble base. The water-soluble base used in the present invention can be easily dissociated into cations (M ⁺ ) and anions (A ⁻ ) in an aqueous solution, thereby increasing the activity of the polyoxyalkylene alkoxide ion formation reaction (the reaction (1)). have. In addition, the non-aqueous organic solvent facilitates the movement of the polyoxyalkylene alkoxide generated in the aqueous solution, increases the contact of the polyoxyalkylene alkoxide and the alkenyl halide in the non-aqueous solution, and effectively removes the heat of reaction generated during the reaction. can do. Therefore, the present invention can be carried out to produce a polyoxy alkylene alkenyl ether even at 0 to 40 ℃ and atmospheric pressure, and problems caused by preparing the polyoxy alkylene alkenyl ether under high temperature and high pressure (for example, , High cost, yield reduction by polymerization of polyoxyalkylene alkenyl ether, etc.). Furthermore, it is possible to produce high yield polyoxy alkylene alkenyl ether at low cost, thereby increasing efficiency and economy.

The non-aqueous organic solvent used in the present invention may be used without limitation as long as it has affinity with the polyoxy alkylene alkoxide and can form the same phase as the alkenyl halide. The non-aqueous organic solvent may be used 100 to 1000 parts by weight per 100 parts by weight of polyoxy alkylene alcohol as a reaction material, for example methylene chloride, acetonitrile, ethyl acetate, methyl ethyl ketone, chloroform, chlorobenzene, dimethyl Polar organic solvents such as acetamide, dimethylformamide, dimethyl sulfoxide and nonpolar organics such as pentane, hexane, heptane, diethyl ether, toluene, benzene, xylene, cyclohexane, cyclopentane, carbon tetrachloride, tetrahydrofuran A solvent is mentioned, These non-aqueous organic solvent can be used individually or in mixture of 2 or more types.

In addition, the alkenyl halide used in combination with the non-aqueous organic solvent may be represented by the following formula (2), 10 parts by weight or more and 100 parts by weight or less may be used per 100 parts by weight of polyoxy alkylene alcohol. 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.

[Formula 2]

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

On the other hand, the water-soluble base constituting the aqueous solution phase in the present invention is not particularly limited, it is preferable that it can be easily dissociated in the aqueous solution phase and have a high reactivity with the polyoxy alkylene alcohol. The base may be used in an amount of 10 parts by weight or more and 100 parts by weight or less per 100 parts by weight of polyoxyalkylene alcohol, and examples thereof include sodium hydroxide, calcium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxylated, potassium methoxylated and methoxylated. Examples thereof include lithium, sodium ethoxylated, calcium ethoxylated, lithium ethoxylated and potassium ethoxylated. These bases can be used individually or in mixture of 2 or more types.

In addition, the aqueous solution phase of the present invention may be composed of 100 to 1000 parts by weight of water per 100 parts by weight of polyoxy alkylene alcohol.

The present invention (a) an aqueous solution containing a polyoxy alkylene alcohol and a water-soluble base; And (b) by introducing the non-aqueous solution containing the non-aqueous organic solvent and the alkenyl halide at the same time or sequentially to prepare a polyoxy alkylene alkenyl ether in high yield, more preferred examples are as follows.

The present invention comprises the steps of: i) introducing water and a water-soluble base into the polyoxy alkylene alcohol; Ii) introducing a non-aqueous solution containing a non-aqueous organic solvent and an alkenyl halide to the aqueous solution of step iii); Iii) optionally performing the reaction by stirring the mixture of step ii) at 0-40 ° C. and atmospheric pressure; Iii) optionally purifying the polyoxy alkylene alkenyl ether from the iii) step product.

In the purification step iii), the product of step iii) is distilled under reduced pressure to remove the non-aqueous organic solvent, water and the excess reaction alkenyl halide, and then the remaining product is filtered to remove salts as reaction by-products. And a first method of removing a water-soluble base that is a surplus reactant; Alternatively, a second method of separating the product of step iii) into an aqueous layer and a non-aqueous layer and distilling the non-aqueous layer may be used to purify the polyoxy alkylene alkenyl ether. In the case of the second method, since the polyoxy alkylene alkenyl ether is also present in the aqueous layer, there is a problem that the yield is reduced by the purification step, the first method is preferred.

The present invention provides a polyoxy alkylene alkenyl ether prepared according to the above production method. At this time, the polyoxy alkylene alkenyl ether may include salts derived from alkenyl halides and water-soluble bases as reaction by-products.

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

100 parts by weight of water and 22 parts by weight of sodium hydroxide (ducksan) were added to 100 parts by weight of MPEG 13 mol (polyoxy alkylene alcohol containing 13 ethoxy, concentrated), and stirred at 300 rpm. To this, 100 parts by weight of hexane and 15 parts by weight of allyl chloride (TCI) were added using a dropping funnel, and the reaction was performed for 5 hours while stirring the mixture at room temperature and atmospheric pressure. Thereafter, the mixture was heated to 80 DEG C, followed by distillation under reduced pressure for 3 hours to remove water, hexane and residual allyl chloride, and a filter to remove residual sodium hydroxide and salts of reaction by-products to remove polyoxyalkylene alkenyl ether. Prepared.

Example  2

Polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 1, except that ethyl acetate was used instead of hexane.

Example 3

A polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 1, except that acetonitrile was used instead of hexane.

Example  4

Polyoxy alkylene ether was prepared in the same manner as in Example 2, except that MPEG 8 mol (polyoxy alkylene alcohol containing 8 ethoxy) was used instead of MPEG 13 mol.

Example  5

Polyoxy alkylene ether was prepared in the same manner as in Example 2, except that MPEG 23 mol (polyoxy alkylene alcohol containing 23 ethoxy) was used instead of MPEG 13 mol.

Comparative Example 1

A polyoxy alkylene alkenyl ether was prepared in the same manner as in Example 1 except that hexane was not used.

Experimental Example

Conversion rates and yields for the polyoxy alkylene alkenyl ethers prepared in Examples 1-5 and Comparative Example 1 are listed in Table 1. In this case, the conversion rate is a value analyzed by LC (Liquid Chromatography). In addition, since the polyoxy alkylene alkenyl ether prepared in Examples 1 to 5 and Comparative Example 1 was purified through distillation under reduced pressure and no loss occurred during the separation process, the yield was the same as the conversion rate. Indicated.

 TABLE 1

division Polyoxy Alkylene
Alcohol Base usage
( Parts by weight ) Allyl chloride
( Parts by weight ) menstruum Reaction time
( hour ) Conversion rate,
Yield (%) Kinds
( EO confiscation) usage
( Parts by weight ) Example 1 13 100 22 15 H ₂ O + C ₆ H ₁₄ 5 100 Example 2 13 100 22 15 H ₂ O + EtOAc 5 100 Example 3 13 100 22 15 H ₂ O + CH ₃ CN 5 100 Example 4 8 100 22 15 H ₂ O + EtOAc 5 100 Example 5 23 100 22 15 H ₂ O + EtOAc 5 100 Comparative Example 1 13 100 22 15 H ₂ O 5 85

In Table 1, when the polyoxyalkylene alkenyl ether was prepared in the ideal system in which the non-aqueous organic solvent was introduced according to the present invention (Examples 1 to 5), the polyoxy alkylene al in the ideal system in which the non-aqueous organic solvent was not introduced. Much higher conversion and yield were obtained compared to the case of preparation of kenyl ether (Comparative Example 1). In addition, it was found that the conversion and yield improvement effects of the present invention were remarkable regardless of the type of non-aqueous organic solvent (Examples 1 to 3) or the carbon length of the polyoxyalkylene alcohol (Examples 4 to 5). From the above, it can be seen that due to the non-aqueous organic solvent introduced in the present invention, the equilibrium of the polyoxy alkylene alkenyl ether formation reaction is shifted to improve the yield of the polyoxy alkylene alkenyl ether.

The present invention can produce a polyoxy alkylene alkenyl ether in high yield, it can be carried out at room temperature (0 to 40 ℃) and atmospheric pressure. Accordingly, the present invention can solve the problems caused by the production of polyoxy alkylene alkenyl ether under high temperature and high pressure, such as a reduction in the yield of polyoxy alkylene alkenyl ether usable as a high cost or polymerizable monomer, Naga can improve efficiency and economics.

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

Claims (13)

(a) an aqueous solution containing a polyoxyalkylene alcohol and a water-soluble base; And (b) A method for producing a polyoxy alkylene alkenyl ether by reacting a non-aqueous organic solvent with a non-aqueous solution containing an alkenyl halide. The method according to claim 1, wherein the aqueous solution and the non-aqueous solution are stirred and reacted. The method according to claim 1, wherein the reaction is carried out at 0 to 40 ° C. and normal pressure. The process of claim 1 further comprising purifying the polyoxy alkylene alkenyl ether formed. The method of claim 4, wherein the purification step is distillation under reduced pressure to remove the non-aqueous organic solvent, water and the alkenyl halide which is a surplus reactant, The method is characterized in that by filtering the resultant (residue) remaining after the distillation, to remove the salt of the reaction by-product and the water-soluble base of the excess reaction material. The method of claim 1, wherein the content of water in the aqueous solution is 100 to 1000 parts by weight per 100 parts by weight of polyoxy alkylene alcohol. The method of claim 1, wherein the content of the water-soluble base is 10 to 100 parts by weight based on 100 weight of the polyoxy alkylene alcohol. The method according to claim 1, wherein the content of the non-aqueous organic solvent is 100 to 1000 parts by weight per 100 parts by weight of the polyoxy alkylene alcohol. The method of claim 1, wherein the alkenyl halide is contained in an amount of 10 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of polyoxy alkylene alcohol. The method of claim 1, wherein the non-aqueous organic solvent is methylene chloride, acetonitrile, ethyl acetate, methyl ethyl ketone, chloroform, chlorobenzene, dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, pentane, hexane, heptane, di A process characterized in that it is selected from the group consisting of ethyl ether, toluene, benzene, xylene, cyclohexane, cyclopentane, carbon tetra chloride and tetrahydrofuran. The method of claim 1, wherein the water-soluble base is 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 consisting of. delete delete

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