KR101171483B1 - Manufacturing method of Glycol mono-tertiary-butylether compound and Glycol mono-tertiary-butylether compound prepared by thereof - Google Patents

Abstract

The present invention relates to a method for preparing a glycol mono-tertiary-butylether compound and to the above-described glycol mono-tertiary-butylether compound, and specifically to a method for preparing a glycol mono-tertiary-butylether compound A catalytic reaction step of reacting a C ₄ hydrocarbon mixture comprising a silver glycol compound and isobutene in the presence of an acidic catalyst; And a recycling step in which the product generated in the catalysis step is circulated, mixed with the glycol compound and isobutene, and introduced into the catalysis step. According to the preparation method of the present invention, the glycol mono-tertiary-butylether compound can be prepared in a high yield using a reaction raw material which is easy to handle and inexpensive under relatively mild conditions.

Description

Manufacturing method of Glycol mono-tertiary-butylether compound and Glycol mono-tertiary-butylether compound prepared by according to the present invention

The present invention relates to a method for preparing a glycol mono-tertiary-butylether compound and to a glycol mono-tertiary-butylether compound produced by the present invention. Specifically, the reaction conditions are not harsh, the handling is easy, and the relatively inexpensive It is not only used for starting material by-product glycol di-tertiary-butyl while minimizing the production of ether compound glycol mono-tertiary-production method of the ether compound-ether compound yield glycol to maximize the-tertiary And to glycol mono-tertiary-butylether compounds produced thereby.

The glycol mono-tertiary - butyl ether compound is a substance which can replace the general glycol mono-butyl ether compound among the components of the stripping liquid used to peel the resist from the substrate in manufacturing processes such as semiconductor devices and liquid crystal display devices. In addition, it can be used as a high boiling point solvent in the field of paint, coating, etc. to give a leveling effect.

Generally, glycol mono-butylether compounds are prepared by the reaction of butyl alcohol and ethylene oxide in the presence of sodium ethoxide catalyst. However, butyl alcohol and ethylene oxide, which are raw materials, are relatively expensive, have a risk of explosion, and have a problem of reacting at high temperature and high pressure. Therefore, recently, a method of synthesizing a glycol mono-tertiary-butyl ether compound by reacting a glycol compound with butene compounds such as isobutene under an acidic catalyst has been implemented. In Chinese Patent No. 1065656, diethylene glycol and isobutene are also reacted to synthesize diethylene glycol mono-pentary-butyl ether. However, the reaction does not occur effectively because the ethylene glycol and butene compounds are not mixed with each other, the di-reactant produced about 15 to 30% of diethylene glycol di-tert-butyl ether as a side reactant, resulting in diethylene glycol mono-terrestrial. There is a problem that the yield of -butyl ether is poor.

In order to solve the above problems, an object of the present invention is not to use harsh reaction conditions, easy to handle and use relatively inexpensive raw materials, and to minimize the formation of by-product glycol di-tertiary-butyl ether compounds while desired products. It is to provide a method for preparing a glycol mono-tertiary-butyl ether compound capable of maximizing the yield of the phosphorus glycol mono-tertiary-butyl ether compound and a glycol mono-tertiary-butyl ether compound produced thereby.

The present invention to achieve the above object

A catalysis step of reacting a C ₄ hydrocarbon mixture including a glycol compound of Formula 1 with isobutene in the presence of an acidic catalyst; And

It provides a method for producing a glycol mono- tert-butyl ether compound of Formula 2 comprising a recycle step of circulating the product produced in the catalysis step is mixed with the glycol compound and isobutene and introduced into the catalysis step do:

<Formula 1>

(In Chemical Formula 1,

R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 1 to 4)

<Formula 2>

(In Chemical Formula 2,

R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 1 to 4.

The product recycled in the recycling step may be recycled in a weight ratio of 1 to 20 times compared to the product that is not recycled.

The production method may further include a by-product circulation step in which a glycol di-tertiary-butylether compound in the product generated in the catalysis step is circulated after the recirculation step and introduced into the catalysis step.

The glycol di-tert-butyl ether may be represented by the following Chemical Formula 3:

<Formula 3>

(In Chemical Formula 3,

R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

n is an integer from 1 to 4.

It may further include a separation step of separating the glycol di- tert-butyl ether compound from the product produced in the catalysis step before the by-product circulation step.

The isobutene may be included in an amount of 10% by weight or more based on the C ₄ hydrocarbon mixture.

The glycol compound and isobutene may be reacted in a molar ratio of 1: 1 to 5: 1.

In order to achieve the other object of the present invention,

Provided is a glycol mono-tertiary-butylether compound prepared by the above method.

The preparation method of the glycol mono-tertiary-butylether compound of the present invention is easy to handle and relatively safe, and because it uses a low-cost raw material, the process is convenient and the product can be produced at low cost. In addition, the reaction can be carried out under relatively harsh conditions.

The production method of the present invention improves the yield of the glycol mono- tert-butyl ether compound as a product, and can minimize the production of the by-product glycol di-tert-butyl ether compound, thereby reducing the cost of the by-product treatment.

The glycol mono-tertiary-butyl ether compound produced by the present invention can be used in the manufacturing process of semiconductor devices, liquid crystal display devices, etc., can also be used as a high boiling point solvent in the field of painting or coating, and leveling properties Can be improved.

1 is a flowchart illustrating a method for preparing a glycol mono-tertiary-butyl ether compound according to an embodiment of the present invention in order.
Figure 2 shows a device and a flow line (Flow line) used in the preparation of the glycol mono- tert-butyl ether compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

1 is a flowchart illustrating a method for preparing a glycol mono-tertiary-butyl ether compound according to an embodiment of the present invention in order. Referring to FIG. 1, the method for preparing a glycol mono-tertiary-butyl ether compound of the present invention may include a catalytic reaction step (S1); Recycling step (S2); Unreacted C ₄ removal step (S3); Separation step S4; And by-product circulation step (S5). The method for preparing the glycol mono-tertiary-butylether compound includes the step of recycling the product to promote the mixing of non-mixing reactants, while recycling the by-products again to reduce the production of by-products and to improve the yield of the desired product. Can be improved.

The catalysis step (S1) is a step in which a C ₄ hydrocarbon mixture including a glycol compound and isobutene is reacted in the presence of an acidic catalyst.

Specifically, a C ₄ hydrocarbon mixture including a glycol compound and isobutene, which are reaction raw materials, may be charged into a catalytic reactor 10 in which an acidic catalyst is packed, thereby performing a catalytic reaction.

The glycol compound may be represented by the following Chemical Formula 1:

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 4. Preferably, diethylene glycol wherein n is 1 may be used.

The C ₄ hydrocarbon mixture including isobutene is C ₄ produced during catalytic cracking of heavy oil in petroleum refining. It can be used alone or a mixture thereof selected from the group consisting of C ₄ residue and isobutene produced during the fractionation or naphtha pyrolysis. Preferably, a mixture containing 10% by weight or more of the isobutene relative to the C ₄ hydrocarbon compound may be used. When the mixture containing the isobutene is contained in less than 10% by weight may lower the yield may lower the reaction efficiency.

The isobutene in the glycol compound and the C ₄ hydrocarbon mixture may be reacted in a molar ratio of 1: 1 to 5: 1, preferably in a molar ratio of 1.5: 1 to 3.0: 1. If the molar ratio of the reaction is less than 1: 1, the reaction efficiency is too low, and if the reaction molar ratio exceeds 5: 1, the cost input up to recycling increases, causing a cost increase.

Preferably, the acidic catalyst may be a strong acid cation exchange resin. The strongly acidic cation exchange resin may be a strong acid cation exchange resin that is preferably insoluble in water having a sulfonic acid group (SO ₃ H) as strong acid, and specifically, a styrene-sulfonic acid cation exchange resin and a phenol-sulfonic acid cation. Exchange resins or crosslinkers thereof, sulfonated coal or sulfonated asphalt, and the like may be used, but are not limited thereto.

The reaction temperature of the catalysis is 30 to 90 ° C, preferably 45 to 65 ° C. If the reaction temperature is less than 30 ℃ reaction rate is slow to reduce the reaction efficiency, if it exceeds 90 ℃ may produce a lot of by-products due to side reactions and the reaction catalyst may be broken or modified.

The pressure of the catalysis may be arbitrarily adjusted by those skilled in the art according to the temperature, and the reaction may be performed at a pressure at which the C ₄ hydrocarbon mixture including isobutene may become a liquid phase. Preferably at 5 to 10 atmospheres. When performed within this pressure range the yield and efficiency of the reaction is increased.

In the catalysis, the reaction raw material may be added to the catalytic reaction at a weight hourly space velocity (WHSV) of 0.1 to 10, and preferably, 0.5 to 3. If less than 0.1, the production efficiency is lowered, if more than 10, the reaction efficiency is lowered.

The glycol mono-tertiary butyl ether produced by the catalytic reaction may be represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2, R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 4. Preferably, n may be diethylene glycol mono-tertiary-butyl ether.

The recycling step (S2) is a step in which the product produced in the catalysis step is circulated, mixed with the glycol compound and isobutene, and introduced into the catalysis step.

The C ₄ hydrocarbon mixture including the glycol compound and isobutene, which are the raw materials for the catalytic reaction, is not mixed well, and thus the progress of the reaction is not easy. However, when circulating a part of the product, the glycol mono-tertiary-butyl ether compound contained in the product mixes the glycol compound which is a raw material and isobutene to facilitate the progress of the reaction.

The recycling may be carried out by a method of circulating a part of the product produced in the catalysis to put it in a catalytic reaction together with the raw material, while obtaining a desired product without circulating another part of the product. Specifically, some of the product passed through the catalytic reactor 10 is mixed with the reaction raw material through the first circulation pipe 11 and re-introduced into the catalytic reactor 10, and part of the product through the product delivery pipe 12, C ₄ May be conveyed to the stripper 20. At this time, the product recycled in the product produced in the catalysis step may be recycled in a weight ratio of 1 to 20 times compared to the product that is not recycled. If the amount of the recycled product is less than 1 times the weight ratio of the non-recycled product, the mixing of raw materials may not be performed, and the reaction may be difficult to proceed.If the weight ratio exceeds 20 times, the side reactions increase, resulting in decreased production efficiency. can do.

The unreacted C ₄ removal step (S3) is a step of separating the unreacted C ₄ hydrocarbon in the product produced by the catalytic reaction.

The C ₄ hydrocarbon mixture, a raw material of the present invention, is a C ₄ produced during catalytic cracking of heavy oil in petroleum refining process including isobutene. A mixture of such C ₄ residue produced in oil or naphtha pyrolysis, isobutene and glycol compound is selectively reacted with the remaining C ₄ hydrocarbons in the C ₄ hydrocarbon mixture from the catalytic reaction step is discharged with the product. Therefore, the unreacted C ₄ hydrocarbons in the product may be separated from the unreacted C ₄ removal step to increase the purity of the product, and the separated unreacted C ₄ hydrocarbons may be reused in other processes.

Separation of the unreacted C ₄ hydrocarbon may be specifically carried out by passing the product of the catalysis through a C ₄ stripper 20, but is not limited thereto and may be separated by a method known in the art. have. Specifically, it may be distilled in the C ₄ stripper to be separated by boiling point difference.

The separation step (S4) is a step of separating the glycol di-tertiary-butyl ether from the product of the catalysis.

Glycol Compounds and Isobutene React Under Acidic Catalysts When glycol compounds react with one isobutene molecule to produce a glycol mono-tertiary-butylether compound, but when reacted with more than one molecule of isobutene, glycol di-tertiary as a byproduct A butyl ether compound is also produced. In the present invention, the by-product glycol di-tert-butyl ether compound is recycled to maximize the yield, and the separation step separates the desired product of glycol mono-tert-butyl ether and recycles the by-product glycol di-tertiary before recycling. Collecting butyl ether.

The glycol di-tert-butyl ether may be represented by the following Chemical Formula 3:

<Formula 3>

In Formula 3, n may be an integer of 1 to 4, R ₁ and R ₂ may be hydrogen or an alkyl group having 1 to 5 carbon atoms. Preferably, n may be diethylene glycol di-tert-butyl ether.

Separation of the glycol di-tert-butylether compound may be carried out by azeotropic distillation. Specifically, the non-recycled product of the product produced in the catalysis step is transferred to the azeotropic distillation column 30 after the unreacted C ₄ hydrocarbon is removed via the C ₄ stripper 20. In the azeotropic distillation column 30, the glycol di-tertiary-butylether compound in the product forms an azeotrope with water to be distilled by boiling point difference and is transferred to the separation tank 40. The product comprising the residue glycol mono-tertiary-butylether compound is separately sent to glycol mono-tertiary-butylether distillation column (60). In the distillation column (60), glycol mono-tertiary-butyl ether is distilled off, and the remaining glycol compound is fed back into the catalytic reactor (10). In the separation tank 40, the glycol di-tertiary-butylether compound and water are separated, and the separated water is circulated to the azeotropic distillation column to supply water to the azeotropic distillation column, and the glycol de-turry Butyl ether is to be transferred to the reservoir (50).

The by-product circulation step (S5) is a step of circulating the glycol di-tertiary-butyl ether compound in the product produced in the catalysis step after the recirculation step to the catalysis step.

Specifically, in the separation step, the glycol di-tertiary-butyl ether compound transferred to the storage tank 50 through the separation tank 40 is circulated and introduced into the catalytic reactor 10 together with the reaction raw material. The yield can be maximized by recycling the by-product glycol di-tert-butylether compound.

In general, when the glycol compound and isobutene react, a glycol mono-tertiary-butyl ether compound and a glycol di-tertiary butyl ether compound are produced in a weight ratio of 85:15 to 70:30. That is, by-product glycol di-tert-butylether compound is produced up to 30% by weight. The reaction in which the glycol di-tert-butyl ether compound is produced is a reversible reaction. When the glycol di-tert-butyl ether compound is produced in excess of 30% by weight, the glycol di-tert-butyl ether compound is a glycol mono-terminator. Conversion to the sherry-butylether compound leaves one molecule of isobutene. The following scheme shows the reversible reaction of diethylene glycol mono-tert-butyl ether and diethylene glycol di-tert-butyl ether.

<Reaction Scheme>

According to the above reaction formula, when diethylene glycol di-tert-butyl ether is produced in excess of 30% by weight, one molecule of isobutene is removed and converted back to diethylene glycol mono-tert-butyl ether. By recycling ethylene glycol di-tertiary-butyl ether, diethylene glycol can react with only one molecule of isobutene to maximize the yield of diethylene glycol mono-tertiary-butyl ether.

Figure 2 shows the apparatus and flow lines used in one embodiment of the present invention. According to Figure 2, the glycol mono- tert-butyl ether compound production apparatus of the present invention is a reactor (10); C4 stripper 20; Azeotropic distillation column 30; Separation column 40; Distillation column 50; And a reservoir 60 of glycol di-tertiary-butyl ether.

A C ₄ hydrocarbon mixture including a glycol compound and isobutene as raw materials is introduced into a catalytic reactor 10 filled with an acidic catalyst through an injection tube, and a catalytic reaction proceeds, and a part of the product is the first circulation tube 11. ) Is recycled to the catalyst reactor 10 together with the reactant material, while a part is transferred to the C ₄ stripper 20 through the product delivery pipe 12 to remove unreacted C ₄ hydrocarbons. The reaction product passed through the C ₄ stripper 20 is transferred to the azeotropic distillation column 30 and the reaction by-product glycol di-tertiary-butylether compound is azeotropically distilled with water introduced into the azeotropic distillation column 30, Water and glycol di-tertiary-butylether compound are sent to a separation tank 40 that separates them. The glycol di-tertiary-butylether compound separated from the water in the separation tank 40 is transferred to the storage tank 50 and collected. The collected glycol di-tertiary-butylether compound is mixed with the reaction raw material through the second circulation pipe 51 and re-introduced into the catalytic reactor 10. The product from which the glycol di-tertiary-butylether compound has been removed is transferred from the azeotropic distillation column (30) to the glycol mono-tertiary-butylether compound distillation column (60), where the glycol mono-tertiary-butylether compound is Distillation is obtained as a compound. The remaining glycol compound is recovered and reintroduced into the reaction raw materials.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. This is for the purpose of illustrating the present invention, and thus the scope of the present invention is not limited thereto.

< Example  1 to 6 and Comparative example  1 to 7>

A strongly acidic cation exchange resin (50 g of amberlite catalyst, a macroporous sulfonated divinylbenzene-crosslinked polystyrene resin), was charged to a double tube reactor having a length of 60 cm and an inner tube diameter of 1/2 inch. At this time, the heat exchange water was circulated to control the reaction heat to the exterior side. The C ₄ hydrocarbon mixture components used in the reaction are shown in Table 1 below, and the raw material transfer was performed using a mass flow controller (MFC). Diethylene glycol mono-tertiary-butyl ether was produced under atmospheric pressure. At this time, the reaction conditions and the total amount of diethylene glycol mono-tertiary-butyl ether produced are shown in Table 2 below.

ingredient Isobutene n-butane 1-butene C-2-butene T-2-butene i-butane content
(weight%) 47.6 10.9 24.7 4.6 9.3 2.9

As shown in Table 2, the reaction does not proceed when the circulation ratio is too small or does not circulate, and when the circulation ratio increases, the side reaction is activated to reduce the total amount of diethylene glycol mono-tertiary-butyl ether produced.

As described above, the present invention can maximize the yield of the product by recycling the by-product glycol di- tert-butyl ether compound as well as recycling the product. In addition, it is possible to use a reaction material that is easier to handle and cheaper than the conventional one, and the reaction conditions are not relatively harsh.

10: catalytic reactor
11: first recycle tube
12: product delivery pipe
20: C ₄ stripper
30: azeotropic distillation column
40: separation tank
50: reservoir
51: second circulation pipe
60: distillation column

Claims (7)

A catalysis step of reacting a C ₄ hydrocarbon mixture including a glycol compound of Formula 1 with isobutene in the presence of an acidic catalyst;
A recycling step in which the product generated in the catalysis step is circulated and mixed with the glycol compound and isobutene and introduced into the catalysis step;
Separating unreacted C ₄ hydrocarbons from the product produced in the catalysis step;
Separating the glycol di-tertiary-butylether compound of Formula 3 from the product produced in the catalysis step; And
Method for producing a glycol mono- tert-butyl ether compound of the formula (2) characterized in that it comprises a by-product circulation step of circulating the separated glycol di- tert-butyl ether compound into the catalytic reaction step:
<Formula 1>

(In Chemical Formula 1,
R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer from 1 to 4.
(2)

(In the formula (2)
R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer from 1 to 4.
(3)

(In Chemical Formula 3,
R ₁ and R ₂ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
n is an integer from 1 to 4. The method of claim 1,
The method of producing a glycol mono- tert-butyl ether compound, characterized in that the recycled product in the recycling step is recycled in a weight ratio of 1 to 20 times compared to the product that is not recycled. delete delete The method of claim 1,
Method for producing a glycol mono- tert-butyl ether compound, characterized in that the isobutene is contained in more than 10% by weight relative to the C ₄ hydrocarbon mixture. The method of claim 1,
Isobutene contained in the glycol compound and the C ₄ hydrocarbon mixture is reacted in a molar ratio of 1: 1 to 5: 1. delete

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