KR20170114269A - Esters of anhydrosugar alcohol with improved color and method for preparing the same - Google Patents

Abstract

The present invention relates to a colorless alcohol-free alcohol ester and a process for preparing the alcohol-free alcohol ester, and more particularly, to a process for producing an alcohol-free alcohol ester having a low yellowness index And it is possible to improve the economical efficiency and stability of the process because toxic decomposition products are not generated in the manufacturing process, and it is possible to omit the distillation process for removing residual acid components, And a process for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an ester-free alcohol ester having an improved color and a method for producing the same. BACKGROUND ART < RTI ID = 0.0 > ESTERS OF ANHYDROSUGAR ALCOHOL WITH IMPROVED COLOR AND METHOD FOR PREPARING THE SAME &

The present invention relates to a colorless alcohol-free alcohol ester and a process for preparing the alcohol-free alcohol ester. More specifically, the present invention relates to a process for producing an alcohol-free alcohol ester having a low yellowness index And it is possible to improve the economical efficiency and stability of the process because toxic decomposition products are not generated in the manufacturing process, and it is possible to omit the distillation process for removing the remaining carboxylic acid component, And a process for producing the same.

Hydrogenated sugar (also referred to as " sugar alcohol ") refers to a compound obtained by adding hydrogen to the reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (wherein n is an integer of 2 to 5 ), And classified into tetritol, pentitol, hexitol and heptitol (C 4, 5, 6 and 7, respectively), depending on the number of carbon atoms. Among them, hexitol having six carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

Anhydrosugar alcohol has a diol form with two hydroxyl groups in the molecule and can be prepared by utilizing hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid- -2012-0066904). Since alcohol-free alcohol is an eco-friendly substance derived from renewable natural resources, there has been much interest for a long time and studies on the manufacturing method have been carried out. Among these alcohol-free alcohols, isosorbide prepared from sorbitol has the widest industrial application currently.

Such ester of anhydrosugar alcohol is used as an emulsifier used for pharmaceuticals, cosmetics, foodstuffs, etc., and various resin processing additives, and it is known that the use thereof is various. However, when used as a resin processing additive, the yellow index (YI) of the produced alcohol-free alcohol ester is high, and studies have been conducted to improve the yellow index.

For example, in the synthesis of sorbitan esters, the use of an alkaline agent, phosphoric acid, or phosphoric acid has been disclosed to improve color (see, for example, JP44-2964). Also primary phosphate _{(hypophosphorous acid, H 3 PO 2} ) to the acid catalyst and the mixed case of using yellowness disclosed a technique for index synthesized Meridian dihydro-hexyl when tolyl diester (dianhydrohexitol diester) of a color enhancement to below 50 bar ( For example, U.S. Patent No. 8129549).

However, since the above-mentioned techniques use 3 equivalents or more of an expensive carboxylic acid in the production of an alcohol-free alcohol ester, the manufacturing cost is increased and unreacted carboxylic acid must be removed through distillation. In addition, according to U.S. Patent No. 4690783, when the phosgene free alcohol ester is prepared by using phosphorus acid as described above, the cost of the catalyst used is high, decomposition occurs during the ester reaction, and toxicity such as phosphine Gas may be generated and the workability may be deteriorated.

Therefore, there is a demand for a process for producing an anhydrosugar alcohol ester having an improved hue with a low yellowness index and an alcohol-free alcohol ester having improved economy and workability.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a process for producing an alcohol-free alcohol ester, An improved alcohol-free alcohol ester having improved color and an improved processability, which can improve the economical efficiency and stability of the process due to no decomposition product, and can eliminate the distillation process for removing the residual carboxylic acid component, And a manufacturing method thereof.

In order to solve the above-mentioned technical problems, the present invention provides a process for producing a polyaniline, which comprises reacting an anhydrosugar alcohol and a carboxylic acid in the presence of phosphorous acid; And neutralizing the reaction product obtained in the reaction step. The present invention also provides a process for producing an alcohol-free alcohol ester comprising the steps of:

According to another aspect of the present invention, there is provided an alcohol-free alcohol ester which is produced by the above method.

According to another aspect of the present invention, there is provided a resin processing additive comprising an anhydrosugar alcohol ester produced by the above method.

According to another aspect of the present invention, there is provided an article comprising the resinous processing additive.

According to another aspect of the present invention, there is provided a resin processed product comprising an anhydrosugar alcohol ester produced by the above method.

The alcohol-free alcohol ester according to the present invention has an improved hue with a lower yellowness index. The process for producing the alcohol-free alcohol ester of the present invention uses less expensive phosphorous acid, The stability can be improved and the distillation step for removing residual acid components can be omitted, and the efficiency of the process can be improved, which is easy to commercialize.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a process for the production of polyphosphoric acid, comprising the steps of: reacting an anhydrosugar alcohol and a carboxylic acid in the presence of phosphorous acid; And neutralizing the reaction product obtained in the reaction step. The present invention also provides a process for producing an alcohol-free alcohol ester comprising the steps of:

The above-mentioned dihydric alcohol generally means any substance obtained by removing one or more water molecules from a compound obtained by adding hydrogen to a reducing end group of a saccharide, which is generally called hydrogenated sugar or sugar alcohol. do.

The alcohol-free alcohol of the present invention may be selected from the group consisting of isosorbide (1,6-dianhydroisorbitol), isomannide (1,6-dianhydromannitol), isoidide (1,6-dianhydroiditol) It may be selected.

Although not particularly limited, the reaction step may be performed in the presence of 1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight of phosphorous acid based on 100 parts by weight of an alcohol without anhydride. When the amount of phosphorous acid is less than 1 part by weight, there is a problem that the color improvement effect is not significant. When the amount of phosphorous acid is more than 15 parts by weight, there is a problem of reduction in yield due to excessive reaction.

The phosphorous acid is preferably added to the reactor together with an anhydrosugar alcohol, a carboxylic acid and an acid catalyst to proceed the reaction. The color change in the esterification of anhydrosugar alcohol is due to the dehydration by-products produced by the high temperature at the beginning of the reaction. These byproducts are presumed to contain a double bond, which is colored by dehydration reaction in the molecule. Once formed, oligomers are formed by intermolecular bonding as the reaction progresses, resulting in a darker color. The phosphorous acid acts to suppress the formation of reaction by-products at the initial stage of the reaction and to control the color during the reaction time. Therefore, in general, there is a difference from the decoloring treatment performed in a post-process. In the case of phosphorous acid, after the reaction is completed, the removal effect on the already formed color material is drastically reduced.

In addition, the above reaction step can be carried out using 1 to 3 equivalents, preferably 1 to 2.5 equivalents, more preferably 1 to 2 equivalents of carboxylic acid with respect to 1 equivalent of an alcohol without an alcohol. When the carboxylic acid is less than 1 equivalent, There is a problem that the reaction is insufficient. When the amount is more than 3 equivalents, the production cost is increased and the acid component such as unreacted carboxylic acid must be removed through distillation, so that there is a problem that additional cost is incurred due to the addition of the step.

The carboxylic acid may be an alkylcarboxylic acid having 2 to 24 carbon atoms, a cycloalkylcarboxylic acid having 4 to 25 carbon atoms, an aromatic carboxylic acid having 7 to 25 carbon atoms, or a mixture thereof, for example, octanoic acid, decanoic acid, Dodecanoic acid, ethanoic acid (acetic acid), propionic acid, butyric acid, pentanoic acid, hexanoic acid, ethylhexanoic acid or a combination thereof.

In the process for producing an alcohol-free alcohol ester of the present invention, the reaction step may be carried out in the presence of an acid catalyst for shortening the reaction time, more specifically, 1 to 20 wt. Preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the resin. When the amount is less than 1 part by weight, there is a problem that the reaction rate is slow, and when it is more than 20 parts by weight, there is a problem that excessive reaction occurs.

Although not particularly limited, the acid catalyst may be selected from inorganic acids such as p-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, and combinations thereof.

The reaction may be carried out at a temperature of 70 to 200 DEG C, a pressure of 10 to 300 torr and an inert gas atmosphere, for example, the inside of the reactor may be replaced with nitrogen.

The reaction solution obtained in the reaction step may be mixed with water, and the step of removing water from the reaction solution may be further performed before the neutralization step is performed. The step of removing water from the reaction solution may be performed by lowering the degree of vacuum and removing water by distillation, but is not limited thereto.

In the neutralization step, the reaction product obtained in the reaction step is neutralized to remove residual acid components, and an alcohol-free alcohol ester can be obtained. In the neutralization step, various kinds of basic materials can be used to neutralize the reactant. The basic material is not particularly limited, and for example, a basic aqueous solution, a solid base and the like can be used.

In the neutralization step, 50 to 150 parts by weight of a basic substance may be supplied to the reactant based on 100 parts by weight of an alcohol-free alcohol to remove the residual acid component. The reaction can be neutralized using, for example, 50 to 150 parts by weight of a basic substance having a pH of 10 to 12 based on 100 parts by weight of alcohol without sugar.

Although there is no particular limitation, after the neutralization step is carried out, there is further added a step of concentrating the reactant to which the basic substance is supplied, removing the residual salt by filtration, and improving the color of the alcohol free alcohol ester .

According to the process for producing an alcohol-free alcohol ester of the present invention, the yield of the alcohol-free alcohol ester can be 85 to 99%, preferably 87 to 97%, more preferably 89 to 97%.

According to another aspect of the present invention, there is provided an anhydrosugar alcohol ester produced by the above method. The dihydric alcohol ester of the present invention may have a yellowness index (YI) of 1 to 50, preferably 3 to 25, more preferably 5 to 15.

According to another aspect of the present invention, there is provided a resin processing additive comprising an anhydrosugar alcohol ester produced by the above method. In the present invention, the term "resin processing additive" means a material which can be added to produce a resin processed product, and the resin processing additive including the alcohol-free alcohol ester is, for example, plasticizers, lubricants, But are not limited to, flame retardants, corrosion inhibitors, thickeners, coalescing agents, surfactants, and the like.

According to still another aspect of the present invention, there is provided an article comprising the resin processing additive. The product may be a plastic composition, a resin composition, a cellulosic composition, a chemical, a medicine, a cosmetic, a composition for human or animal food, etc., and the resin processing additive may be used have.

According to another aspect of the present invention, there is also provided a resin processed product comprising an anhydrosugar alcohol ester produced by the above method. In the present invention, the term "processed resin product" means a molded product obtained by extrusion, injection, or other processing using a resin.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[Example]

<Purity analysis>

Purity analysis of the prepared ISB ester was performed using gas chromatography (GC) equipped with a flame ionization detector. Helium was used as the carrier gas, and a non-polar column was used as the column type. The composition of the product was expressed by the area ratio on the chromatogram.

< Yellowness index  (Yellowness Index) measurement>

The yellowness index was measured according to ASTM D1925 using a colorimeter.

[Example 1]

Isosorbide (ISB) 73g, octanoic acid 1- (1-Octanoic acid) 140.5g ( 1.95 eq.), P- toluene sulfonic acid monohydrate 3.6g (compared to 5 wt% ISB) and phosphorous acid (H ₃ PO ₃₎ 2.2 g (3 wt% based on ISB) was fed to a batch reactor connected to a condenser and a condenser. Thereafter, the inside of the reactor was replaced with nitrogen to block oxygen inflow into the reactor. The internal temperature of the reactor was gradually raised to 75 DEG C, the reaction was melted, and the temperature was gradually raised until the internal temperature reached 130 DEG C while maintaining the internal pressure at 90 torr. At this time, as the reaction progresses, the water produced is collected through the cooler. When the produced water was more than 80% of the theoretical value, the internal pressure was gradually lowered to 20 torr or lower, and water was removed from the reaction solution as much as possible to complete the reaction.

After the reaction was completed, the reaction solution was cooled to 80 DEG C while keeping contact with air at a maximum. NaCl aqueous solution containing 5 wt% NaOH was added to the cooled reaction solution, and the mixture was stirred for several minutes, and the mixture was allowed to stand for layer separation, and the aqueous layer was separated. NaCl aqueous solution was added thereto, and the mixture was stirred for several minutes, and then allowed to stand to separate layers. After separating the aqueous layer, the organic layer was concentrated to remove residual water, and the resulting salt was removed by filtration. Purity analysis and yellowness index measurement were carried out in the following manner. The purity measured by gas chromatography was 92.3% for ISB diester and 7.2% for ISB monoester. The yellowness index (YI) was 10.0 and the yield was 89%.

[Example 2]

The procedure of Example 1 was repeated, except that 168.0 g (1.95 eq.) Of 1-decanoic acid was used instead of 1-octanoic acid. At this time, the purity measured by the gas chromatograph method was 92.0% of ISB diester and 7.3% of ISB monoester. YI was 11.3 and yield was 90%.

[Comparative Example 1]

The procedure of Example 1 was repeated except that phosphorous acid (H ₃ PO ₃ ) was not added. In this case, the purity measured by the gas chromatograph method was 92.0% of ISB diester and 7.4% of ISB monoester. YI was 95.0 and the yield was 88%.

[Comparative Example 2]

The procedure of Example 1 was repeated except that phosphoric acid (H ₃ PO ₂ ) was used instead of phosphorous acid. There is a problem that odor remains after the completion of the reaction and washing with the neutralizing liquid. The purity measured by gas chromatography was 91.8% for ISB diester and 7.5% for ISB monoester. YI was 10.3 and the yield was 88%.

The isosorbide esters of Examples 1 and 2 prepared by adding the phosphorous acid by the method of the present invention had an improved hue with a yellowness index of 15 or less and a high yield of 89% or more. However, Comparative Example 1 in which phosphorous acid was not added had a significantly higher 95.0 yellowness index than Examples 1 and 2. In addition, in Comparative Example 2 using phosphorous acid, the yellowness index showed a low value, but toxic gas was generated, and the workability was deteriorated.

Claims (17)

A reaction step of reacting an anhydrosugar alcohol and a carboxylic acid in the presence of phosphorous acid; And
And neutralizing the reactant obtained in said reaction step. The process for producing an alcohol-free alcohol ester according to claim 1, wherein the reaction step is carried out in the presence of 1 to 15 parts by weight of phosphorous acid based on 100 parts by weight of an alcohol free of alcohol. The process according to claim 1, wherein the reaction step is carried out using from 1 to 3 equivalents of carboxylic acid to 1 equivalent of an alcohol free of alcohol. The process according to claim 1, wherein the anhydrosugar alcohol is selected from isosorbide, isomannide, isoidide, or combinations thereof. The process according to claim 1, wherein the carboxylic acid is selected from octanoic acid, decanoic acid, dodecanoic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, ethylhexanoic acid or a combination thereof. . The process according to claim 1, wherein the reaction step is further carried out in the presence of an acid catalyst. 7. The process according to claim 6, wherein the reaction step is carried out using 1 to 20 parts by weight of an acid catalyst based on 100 parts by weight of an alcohol free of alcohol. 7. The process of claim 6, wherein the acid catalyst is selected from p-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, and combinations thereof. The process according to claim 1, wherein the reaction step is carried out in an inert gas atmosphere at a temperature of 70 to 200 DEG C, a pressure of 10 to 300 torr, and an inert gas atmosphere. The method according to claim 1, wherein neutralizing the reactant is carried out using 50 to 150 parts by weight of a basic aqueous solution having a pH of 10 to 12 based on 100 parts by weight of an alcohol-free alcohol as a reactant. The process for producing an alcohol-free alcohol ester according to claim 1, wherein the yield of the alcohol-free alcohol ester is 85 to 99 mol%. 12. An alcohol-free alcohol ester which is produced by the process of any one of claims 1 to 11. 12. A resin processing additive comprising an anhydrosugar alcohol ester prepared by the process of any one of claims 1 to 11. 14. The resin processing additive according to claim 13, which is any one selected from the group consisting of a plasticizer, a lubricant, a flame retardant, an antirust agent, a thickener and a compound. A product comprising the resinous processing additive of claim 13. 16. The product of claim 15, wherein the composition is selected from the group consisting of a plastic composition, a resin composition, a cellulosic composition, a chemical, a medicament, a cosmetic, and a composition for human or animal food. 12. A processed resin product comprising an anhydrosugar alcohol ester prepared by the process of any one of claims 1 to 11.