KR102076134B1 - Method for preparing butyl carbitol formal and butyl carbitol formal prepared by the same - Google Patents

Abstract

The present invention relates to a method for preparing butyl carbitol foam and a butyl carbitol foam produced by the same. Mixture manufacturing step of mixing to prepare a mixture; A vacuum reaction step of reducing the water content of the mixture by reacting the mixture in a vacuum; A cooling step of cooling the mixture; And a deoxidation treatment step of deacidification of the mixture into an aqueous basic solution.
According to the present invention, butyl carbitol foam can be produced in a fast process and in high yield.

Description

METHOD FOR PREPARING BUTYL CARBITOL FORMAL AND BUTYL CARBITOL FORMAL PREPARED BY THE SAME

The present invention relates to a method for preparing butyl carbitol foam and a butyl carbitol foam prepared therefrom, and more particularly, a method for preparing a butyl carbitol foam having a shorter production time and a higher yield, and a butyl produced therein. It relates to carbitol foam.

Plasticizer is an additive that increases the flexibility and elasticity of rubber products. It allows the polymer to be processed below the decomposition point of the polymer to increase the processability of the polymer or the mechanical properties of the polymer, such as the flexibility of the polymer. Used to increase

For example, electrical and electronic products, pharmaceuticals, paint pigments, lubricants, binders, surfactants, adhesives, floor tiles, food container packaging, perfumes, liquid soaps, hair sprays, etc. are very versatile, but some phthalate plasticizers As it is known as a substance that can cause environmental pollution and endocrine disorders in humans, efforts to reduce the damage are strengthening the use regulations in developed countries such as Europe and the United States. Accordingly, research on plasticizer compositions such as terephthalate-based, adipate-based, and other polymer-based compounds that can replace phthalate-based plasticizers is continuing.

Therefore, an object of the present invention is to provide a method for producing butyl carbitol foam having excellent process efficiency and yield.

In addition, it is an object to provide a method for producing butyl carbitol foam that can improve the problem of environmental pollution.

In order to achieve the above object, a method for producing butyl carbitol foam according to an embodiment of the present invention is a mixture preparation step of preparing a mixture by mixing paraformaldehyde (paraformaldehyde) and butyl diglycol (butyl diglycol); A vacuum reaction step of reducing the water content of the mixture by reacting the mixture in a vacuum; A cooling step of cooling the mixture; And a deacidification step of deacidification of the mixture into a basic aqueous solution.

In the preparing of the mixture, the paraformaldehyde and the butyl diglycol may be mixed and then reacted at normal pressure.

In the preparation of the mixture, the butyl diglycol may be 110 to 500 parts by weight based on 100 parts by weight of the paraformaldehyde.

In the preparation of the mixture, the acid value of the mixture may be 5 or less.

The vacuum reaction step may be performed at a temperature of 160 to 250 ℃.

In the vacuum reaction step, the water content of the mixture may be reduced to 0.5% by weight or less.

The acid value of the mixture whose water content is reduced through the vacuum reaction step may be 0.5 or less.

The cooling step may be cooled to 100 ℃ or less.

The deoxidation treatment step may be deoxidized so that the acid value of the mixture is 0.3 or less.

In the deoxidation treatment step, the basic aqueous solution may include an aqueous sodium hydroxide solution.

After the deoxidation treatment step, it may further comprise the step of washing and drying the mixture.

Butyl carbitol foam according to an embodiment of the present invention can be prepared by the method described above.

According to the present invention, in the production of butyl carbitol foam, it is possible to reduce environmental pollution by preparing without using toluene.

In addition, by performing the vacuum reaction step to reduce the residual water content it is possible to reduce the process time required for the deoxidation treatment to increase the production efficiency.

In addition, by reducing the amount of the basic aqueous solution used in the deoxidation treatment, the generation of waste can be reduced and the yield of butyl carbitol foam is greatly improved.

The effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

1 is a flow chart sequentially showing a method for producing butyl carbitol foam according to an embodiment of the present invention.

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various different forms, and the present embodiments merely make the disclosure of the present invention complete, and those of ordinary skill in the art to which the present invention belongs. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims. Like reference numerals refer to like elements throughout.

Unless otherwise defined, all terms used in the present specification (including technical and scientific terms) may be used in a sense that can be commonly understood by those skilled in the art. In addition, the terms defined in the commonly used dictionaries are not ideally or excessively interpreted unless they are specifically defined clearly.

Hereinafter, the manufacturing method of the butyl carbitol foam of this invention, and the butyl carbitol foam manufactured by it are demonstrated in detail.

A method for preparing butyl carbitol foam according to an embodiment of the present invention will be described with reference to FIG. 1.

Referring to Figure 1, the method for producing butyl carbitol foam according to an embodiment of the present invention includes a mixture preparation step (S10), vacuum reaction step (S20), cooling step (S30) and deoxidation treatment step (S40). do.

Mixture manufacturing step (S10) is a step of mixing paraformaldehyde (paraformaldehyde) and butyl diglycol (butyl diglycol), a process for mixing the raw material of butyl carbitol foam to prepare a mixture.

Butylcarbitol foam is a material that can give low temperature flexibility to various kinds of elastomers including natural rubber, styrene butadiene rubber (SBR), chloroprene, nitrile and epichlorohydrin. -Butoxyethoxy) ethoxy) methane (Bis (2- (2-butoxyethoxy) ethoxy) methane).

The butyl diglycol may be 110 to 500 parts by weight, and preferably 150 to 200 parts by weight based on 100 parts by weight of the paraformaldehyde. Outside the range of the paraformaldehyde, there may be a problem that the physical properties and yield of the produced butyl carbitol foam is lowered or the raw material is used excessively.

The mixture may further include additives such as acid catalysts and anti-colorants, and the additive may be 1 to 10 parts by weight based on 100 parts by weight of the mixture.

The mixture preparation step may be carried out in an atmosphere consisting of at least one inert gas of nitrogen gas or hydrogen gas at atmospheric pressure, preferably, may be reacted by mixing paraformaldehyde and butyl diglycol under the introduction of nitrogen gas. The acid value of the mixture in the mixing step may be 5 or less. When the acid value is 5 or less, the acid value is continuously lowered through the subsequent process to produce butyl carbitol foam having a desired acid value.

Vacuum reaction step (S20) is a step for reacting the mixture in a vacuum, a process for reducing the water content of the mixture prepared in the mixture production step (S10).

After performing the atmospheric pressure reaction in the mixture preparation step (S10), by reacting in a vacuum state it is possible to significantly lower the amount of water contained in the mixture. The vacuum pressure may preferably be 400 to 600 mm Hg. If the vacuum pressure is less than 400mHg, sufficient water removal is not achieved. If the vacuum pressure is higher than 600mHg, the high pressure may change the physical or chemical properties of the mixture.

The mixture in the mixture preparation step (S10) has a water content of about 2% by weight, and after the vacuum reaction step (S20), the water content may drop to 0.5% by weight or less, preferably 0.2% by weight or less. That is, by carrying out a further vacuum reaction step, the water content of the mixture can be significantly lowered. If the water content exceeds 2% by weight, it is difficult to remove a lot of water contained in the mixture, even if removed, the amount of the final residual water may be inhibited physical properties of the butyl carbitol foam.

When the water content of the mixture drops to 0.5% by weight, preferably 0.2% by weight, the temperature can be raised to recover the solvent. At this time, the temperature may be 100 to 200 ° C, preferably 120 to 150 ° C. Solvent recovery rate according to an embodiment of the present invention can be improved by 5 to 15% compared to the conventional, there is an advantage that the solvent can be recycled.

Cooling step (S30) is a step of cooling the mixture prepared through the vacuum reaction step (S20).

The acid value of the mixture prepared from the vacuum reaction step (S20) is 0.2 or less, it can be cooled when the water content of the mixture is 0.2% by weight or less, preferably 0.1% by weight or less.

Cooling step (S30) may be cooled to 100 ° C or less, preferably to 80 ° C or less.

Deacidification step (S40) is a step of deacidification of the mixture prepared in the cooling step (S30) with a basic aqueous solution (deacidification), it is possible to lower the acid value of the mixture.

The basic aqueous solution may be an aqueous solution containing an alkali metal or an alkaline earth metal, and specifically, any one of potassium hydroxide, sodium hydroxide, calcium hydroxide or lithium hydroxide may be used alone or in combination of two or more thereof. Preferably it may include an aqueous sodium hydroxide solution.

In the deoxidation treatment step (S40), the acid value of the mixture may be deoxidized to 0.3 or less, and preferably, 0.1 or less.

Through the vacuum reaction step (S20), the cooling step (S30) and the deoxidation step (S40), since the water content and acid value of the mixture is lowered, the amount of the basic aqueous solution can be reduced, thereby reducing waste generation and yield Can greatly improve. In addition, when the acid value of the mixture exceeds 0.3 may cause a problem that does not increase the flexibility and elasticity of the product when used as a plasticizer.

After the deoxidation treatment step (S40), it may further comprise the step of washing and drying the mixture.

In the washing, the washing water is added, the mixture is stirred for 15 minutes to 3 hours, and then, the washing is performed to separate the produced soap and the washing water, and the washing water is added again to remove impurities remaining in the mixture. A second washing step may be included. The second washing step may also be carried out by stirring for 15 minutes to 3 hours, followed by standing still, and then removing the separated wash water.

After washing, it can be dried to remove moisture remaining in the mixture. The drying method may be a vacuum dewatering method. Specifically, the temperature of the reactor may be raised to 80 to 150 ° C. to remove moisture by vacuum decompression under an inert gas atmosphere.

Through the drying process, the water-free mixture can be cooled and filtered. Since the amount of the basic aqueous solution used in the deoxidation treatment step (S40) is small, the filtration time can be shortened.

Butyl carbitol foam according to an embodiment of the present invention can be prepared by the method described above.

The following is an experimental result carried out to demonstrate the superiority of the method for producing butyl carbitol foam of the present invention and the butyl carbitol foam prepared therefrom.

Example

In a 250 ml four-necked round flask, 20 g of paraformaldehyde in a total amount of 200 g, 179 g of butyl diglycol, 0.1 g of an acid catalyst, 1.1 g of a coloring agent were added, and the temperature was raised to 120 to 160 ° C., about 12 to 15 hours 1 The reaction was carried out. At this time, dehydration was carried out in a vacuum reaction at 0.2 wt% of water and an acid value of 3 or less, and the acid value was lowered. When the water content was less than 0.1% by weight, the temperature was raised to 200 to 210 ° C to recover the vacuum solvent. Chromatographic analysis after solvent recovery, the result of cooling to less than 0.1% of free alcohol to 80 to 90 ℃ neutralized with aqueous sodium hydroxide solution. After neutralization, the remaining water remaining in the reactor was washed with water at 90 to 100 ° C. through water washing. After cooling, the resultant was filtered to obtain a yield. Filtration was performed smoothly without generating pressure.

Comparative example

Into a 250 ml four-necked round flask, 16.1 g of paraformaldehyde, 19 g of toluene, and 161.2 g of butyldiglycol were added in a total volume of 200 g. The first reaction was carried out for 12 hours to 15 hours. At this time, it cooled at 0.2 weight% of moisture and acid value 1 or less. The reaction water was about 9.6 g and the recovered toluene was 18 g. The mixture was cooled to 80 to 90 ° C., 1.6 g of sodium carbonate was added thereto, 0.8 g of water was added, and solvent recovery was performed at 200 to 210 ° C. Chromatographic analysis after solvent recovery showed less than 0.1% free alcohol. This was filtered to find the yield. Filtration was slow due to sodium carbonate, and the filtration residue was frequently removed, which required a long time for filtration.

The yield of the butyl carbitol foam prepared by the Example and the comparative example was measured, and it is shown in Table 1 below.

Example Comparative example Yield of Butyl Carbitol Form 61% 55%

Referring to Table 1, the yield of butylcarbitol foam was improved by 6% in comparison with the comparative example. In addition, the reaction time and the filtration time is reduced to obtain butyl carbitol foam in a short time compared to the comparative example. Specifically, since the comparative example is deoxidized using sodium carbonate, the filtration rate and the efficiency are lowered, and thus the yield is lowered.

In addition, the manufacturing method according to the embodiment does not use toluene as a raw material to ensure the safety of the process, there is an advantage that can reduce the environmental pollution.

The scope of the present invention is not limited to the above-described embodiments but may be implemented in various forms of embodiments within the scope of the appended claims. Without departing from the gist of the invention as claimed in the claims, any person of ordinary skill in the art to the present invention is considered to be within the scope of the claims described in the scope of the present invention to various modifications.

Claims (12)

A mixture preparation step of preparing a mixture having an acid value of 5 or less by mixing paraformaldehyde and butyl diglycol;
Reacting the mixture in vacuo to reduce the water content of the mixture, wherein the acid value of the mixture with reduced water content is 0.5 or less;
A cooling step of cooling the mixture; And
A deoxidation treatment step of deacidification with a basic aqueous solution so that the acid value of the mixture is 0.3 or less.
The method of claim 1,
The mixture manufacturing step,
After the paraformaldehyde and the butyl diglycol are mixed, the method for producing butyl carbitol foam, characterized in that the reaction at normal pressure.
The method of claim 1,
In the preparation of the mixture,
The butyl diglycol is a method for producing butyl carbitol foam, characterized in that 110 to 500 parts by weight based on 100 parts by weight of the paraformaldehyde.
delete The method of claim 1,
The vacuum reaction step is a method for producing butyl carbitol foam, characterized in that carried out at a temperature of 160 to 250 ℃.
The method of claim 1,
Method for producing a butyl carbitol foam, characterized in that the water content of the mixture in the vacuum reaction step is reduced to 0.5% by weight or less.
delete The method of claim 1,
The cooling step is a method for producing butyl carbitol foam, characterized in that the cooling to 100 ℃ or less.
delete The method of claim 1,
In the deoxidation treatment step,
The basic aqueous solution is a method for producing butyl carbitol foam, characterized in that it comprises an aqueous sodium hydroxide solution.
The method of claim 1,
After the deoxidation treatment step,
Method for producing a butyl carbitol foam characterized in that it further comprises the step of washing and drying the mixture.


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