KR20170070313A - Improved manufacturing process of esters of anhydrosugar alcohol - Google Patents
Improved manufacturing process of esters of anhydrosugar alcohol Download PDFInfo
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- KR20170070313A KR20170070313A KR1020150176803A KR20150176803A KR20170070313A KR 20170070313 A KR20170070313 A KR 20170070313A KR 1020150176803 A KR1020150176803 A KR 1020150176803A KR 20150176803 A KR20150176803 A KR 20150176803A KR 20170070313 A KR20170070313 A KR 20170070313A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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Abstract
The present invention relates to a process for producing an alcohol-free alcohol ester, and more particularly, to a process for producing an alcohol-free alcohol ester by using an intermediate product of a sugar alcohol dehydration reaction, The present invention relates to a process for producing an alcohol-free alcohol ester which is advantageous for mass production and commercialization because it is an economical process which improves the ester reaction rate and completeness and does not deteriorate the purity and yield even when the unreacted fatty acid is recovered by distillation and then reused.
Description
The present invention relates to a process for producing an alcohol-free alcohol ester, and more particularly, to a process for producing an alcohol-free alcohol ester by using an intermediate product of a sugar alcohol dehydration reaction, The present invention relates to a process for producing an alcohol-free alcohol ester which is advantageous for mass production and commercialization because it is an economical process which improves the ester reaction rate and completeness and does not deteriorate the purity and yield even when the unreacted fatty acid is recovered by distillation and then reused.
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.
The dianhydrosugar alcohol (hereinafter referred to as anhydrous alcohol) has a diol form having two hydroxyl groups in the molecule and can be prepared by utilizing dehydration reaction of hexitol derived from starch (for example, Korean Patent No. 10- Korean Patent Laid-Open Publication No. 10-906618). 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 esters of anhydrosugar alcohols are used as various emulsifying agents, preservatives, lubricants, polymerization stabilizers, plasticizers, and the like used in pharmaceuticals, cosmetics, foodstuffs, and the like.
The general process for the production of anhydrosugar alcohol esters is based on the direct ester reaction between anhydrosugar alcohol and carboxylic acid in the presence of an acid catalyst. As an acid catalyst, it is common to use a low-cost inorganic acid having good reactivity, but a technique of producing an ester improved in color using a solid acid or an acidic ion-exchange resin has also been reported (for example, Korean Patent Publication No. 10-2003-0004382 ).
Another aspect of improving the process for the production of anhydrous alcohol esters is to develop an economical process with reduced production costs. Reducing production costs will lead to market expansion of products using environmentally friendly materials, which will ultimately lead to the development of carbon abatement and sustainable materials. However, if it is proved that there is no deterioration of physical properties even if the raw material is changed at this time, the market competitiveness can be secured. The manufacturing process that has been developed to date is still inferior in terms of market competitiveness due to high raw material costs and high processing costs.
Therefore, there is a continuing need for studies on a process for producing an alcohol-free alcohol ester which is economical and has excellent physical properties.
It is an object of the present invention to provide a process for producing an alcohol-free alcohol ester, which comprises using an intermediate product of a sugar alcohol dehydration reaction, without deteriorating physical properties of an alcohol-free alcohol ester as an end product and increasing an ester reaction rate and integrity using an excess of fatty acid , Unreacted fatty acid is an economical process which does not deteriorate purity and yield even when it is recovered by distillation and then reused, thereby providing a process for producing an alcohol-free alcohol ester which is advantageous for mass production and commercialization.
In order to accomplish the above object, the present invention provides a process for producing an alcohol-free alcohol, comprising the steps of: (1) dehydrating a sugar alcohol to obtain an intermediate product of an alcohol- (2) synthesizing an alcohol-free alcohol ester by esterifying an intermediate product of the reaction for producing an alcohol-free alcohol obtained in the step (1) above with an excess of carboxylic acid; (3) neutralizing a mixture comprising the alcohol-free alcohol ester and the unreacted carboxylic acid obtained as a result of the step (2), with a basic substance; And (4) distilling the neutralized mixture containing the alcohol-free alcohol ester and the unreacted carboxylic acid obtained as a result of the step (3), and recovering the unreacted carboxylic acid therefrom, to provide.
According to another aspect of the present invention, there is provided an anhydrosugar 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.
According to the process for producing the alcohol-free alcohol ester of the present invention, the intermediate product of the sugar alcohol dehydration reaction is used, and the physical properties of the alcohol-free alcohol ester as the final object are not lowered, the ester reaction rate and completeness are increased by using the excess fatty acid, Unreacted fatty acids are advantageous for mass production and commercialization of alcohol-free alcohol esters because they have an economical efficiency in that purity and yield are not lowered even after being recovered by distillation and then reused.
Hereinafter, the present invention will be described in more detail.
The method for producing an alcohol-free alcohol ester of the present invention comprises a step of dehydrating a sugar alcohol to obtain an intermediate product of the alcohol-free alcohol production reaction (step (1)).
Anhydrous alcohol is 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, generally referred to as hydrogenated sugar or sugar alcohol .
The intermediate product of the above alcohol-free alcohol production reaction means one or more substances or mixtures thereof added or produced in the dehydration reaction, which is a production step of anhydrous alcohol. More specifically, it means a sugar alcohol as raw material, an alcoholic alcohol having one molecule removed from water molecule, or an imidazole alcohol having two water molecules removed, or a mixture of two or more thereof.
The sugar alcohol (hydrogenated sugar) generally has the formula HOCH 2 (CHOH) n CH 2 OH (wherein n is an integer of 2 to 5), and depending on the number of carbon atoms, tetritol, pentitol, hexitol and heptitol (4, 5, 6 and 7 carbon atoms, respectively). Among them, hexitol having six carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like. In one embodiment, the sugar alcohol may be selected from sorbitol, mannitol, iditol, and combinations thereof.
As the sugar alcohol used as a raw material in the present invention, it is appropriate to use a sugar alcohol having a sugar alcohol content of 60 to 99% by weight from the viewpoint of economy of the process.
The term " alcoholic alcohol " means any substance from which one water molecule has been removed from the sugar alcohol, and may be selected from sorbitan, mannitine, edidans, and combinations thereof.
The dianhydrides alcohols include isosorbide (1,4: 3,6-dianhydroisorbitol), isomannide (1,4: 3,6-dianhydromannitol), isoidide (1,4: 3,6 -Dianhydroiditol), and combinations thereof.
The solids content of the intermediate product of the alcohol-free alcohol production reaction may be, for example, 70 to 98.5% by weight, more specifically 90 to 98.5% by weight, and more particularly 95 to 98.5% by weight.
In addition, the water content of the intermediate product in the alcohol-free alcohol producing reaction may be, for example, 1.5 to 30 wt%, more preferably 1.5 to 10 wt%, and even more preferably 1.5 to 5 wt%. Water has a lower water content because it causes a reverse reaction to slow the reaction and lower the reaction efficiency. However, if the water content of the intermediate product of the alcohol-free alcohol production reaction is lower than 1.5% by weight, the economical efficiency of the process becomes low.
The intermediate product of the alcohol-free alcohol production reaction may include 10 to 40% by weight, more preferably 15 to 35% by weight, based on 100% by weight of the solid content. If the content of dianhydrosugar alcohol in the intermediate product of the alcohol-free alcohol production reaction is higher than the above range, the economical efficiency may be lowered, and if it is less than this range, the alcohol content of the diol alcohol may be relatively increased, There may be a problem of lowering. The alcohol content in the intermediate product of the alcohol-free alcohol producing reaction may be 60 to 90% by weight, or 65 to 85% by weight based on 100% by weight of the solid content.
An acid catalyst is preferably used for the dehydration reaction of the sugar alcohol.
According to one embodiment, the acid catalyst is selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, And more preferably, sulfuric acid and another acid (for example, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or aluminum sulfate) may be mixed and used. The amount of the acid catalyst to be used is preferably 0.5 to 10 parts by weight per 100 parts by weight of the sugar alcohol (e.g., hexitol).
The method for producing an alcohol-free alcohol ester of the present invention comprises a step of esterifying an intermediate product of the reaction for producing an alcohol-free alcohol obtained in the above step (1) with an excess of carboxylic acid to synthesize an alcohol-free alcohol ester [ )step].
In the esterification reaction step, excess carboxylic acid is used to increase the reaction rate with the intermediate product of the alcohol-free alcohol production reaction and the completion of the reaction. The unreacted carboxylic acid that has not participated in the reaction is effectively removed and reused in the subsequent distillation step to minimize the occurrence of additional costs.
Therefore, in the esterification reaction step, 1.5 to 10 equivalents, preferably 1.5 to 5 equivalents, more preferably 1.5 to 3 equivalents of carboxylic acid can be used per 1 equivalent of the intermediate product of the alcohol-free alcohol production reaction.
Although not particularly limited, 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. Examples thereof include octanoic acid, decanoic acid, Dodecanoic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, ethylhexanoic acid, and combinations thereof.
In the process for producing an alcohol-free alcohol ester of the present invention, the esterification reaction step may be carried out in the presence of an acid catalyst in order to shorten the reaction time. More specifically, 100 parts by weight of the intermediate product of the alcohol- 1 to 20 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight of an acid catalyst. If the amount of the acid catalyst used is less than the above amount, there is a problem that the reaction rate is slow, and if it is more than that, there is a problem that excessive reaction occurs.
Although not particularly limited, the acid catalyst may be an inorganic acid, more specifically, p-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, or a combination thereof.
In the esterification reaction step, an optional color control agent is added in an amount of 1 to 15 parts by weight based on 100 parts by weight of the intermediate product of the alcohol-free alcohol production reaction in order to inhibit the generation of chromogenic materials that can be generated at high temperatures .
The esterification reaction step may be performed at a temperature of 70 to 200 DEG C, a pressure of 10 to 300 torr, and an inert gas atmosphere, for example, by replacing the gas inside the reactor with nitrogen.
The product obtained in the esterification reaction step may be one in which a carboxylic acid is combined with one molecule to a maximum of six molecules in the form of a sugar alcohol, a dianhydrosugar alcohol, and an ester compound capable of being formed by reaction of dianhydrosugar alcohol with a carboxylic acid .
The result obtained in the esterification reaction step may be in a liquid state mixed with water, and the step of removing water from the reaction liquid may be further performed before or after the subsequent neutralization step is performed. The step of removing water from the esterification reaction product may be carried out by lowering the degree of vacuum and removing water by distillation, but is not limited thereto.
The method for producing an alcohol-free alcohol ester of the present invention comprises neutralizing a mixture containing an alcohol-free alcohol ester and an unreacted carboxylic acid obtained as a result of the step (2), with a basic substance [step (3)].
In the neutralization step, the acid component remaining in the resulting mixture obtained in the esterification reaction step may be neutralized and removed. Various types of basic materials may be used in the neutralization step. As the basic substance, for example, a basic aqueous solution, a solid base and the like can be used, and more specifically, a hydroxide of an alkali or an alkaline earth metal (for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.) A base selected from a compound (e.g., triethylamine, ethyldimethylamine, ammonia and the like), a carbonate compound of an alkali or alkaline earth metal (for example, sodium carbonate, potassium carbonate, calcium carbonate, etc.), and combinations thereof, Can be used.
The amount of the basic substance used in the neutralization step may be, for example, 10 to 150 parts by weight based on 100 parts by weight of the intermediate product of the alcohol-free alcohol production reaction, but is not particularly limited thereto. According to one specific example, 10 to 150 parts by weight of a basic substance having a pH of 10 to 12, based on 100 parts by weight of the intermediate product of the alcohol production reaction, may be used to neutralize the resultant mixture of step (1). As a result of the neutralization step, the pH of the mixture can be, for example, from 6 to 8, and if the pH is less than 6 or more than 8, the ester is re- It can be decomposed into alcohol and carboxylic acid.
According to one embodiment, there is added, but not limited to, the step of concentrating the resulting mixture, filtering out the remaining salt by filtration and improving the color of the free alcohol ester reactant after the neutralization step is performed Lt; / RTI >
The process for producing an alcohol-free alcohol ester of the present invention comprises distilling a neutralized mixture containing an alcohol-free alcohol ester and an unreacted carboxylic acid obtained as a result of the step (3) and recovering unreacted carboxylic acid therefrom 4) Step].
The unreacted carboxylic acid in the resulting product after the neutralization step is recovered by distillation. There is no particular limitation on the distillation method of the unreacted carboxylic acid, and known methods and apparatuses known in the art can be used as is or modified appropriately. For example, a general condenser type distiller or distillation tower still can be used, or a thin film still can be used.
The carboxylic acid recovered in the distillation step can be reused in the step (2).
According to one embodiment, the concentration of the unreacted carboxylic acid recovered by distillation in the step (4) is preferably 80 to 98% by weight, more preferably 85 to 95% by weight. If the concentration of the carboxylic acid recovered in step (4) is within the above range, even if the recovered carboxylic acid is immediately reused in the step (2) without any additional treatment such as purification, the quality of the reaction product using the re- It is possible to produce an end product having a uniform quality. On the other hand, if the concentration of the unreacted carboxylic acid recovered is excessively lower than the above level, the new carboxylic acid should be additionally used, so that the economical efficiency of the whole process may be lowered. If the concentration is too high, The economical efficiency of the system can be lowered.
The result of the distillation-free alcohol-free alcohol ester can be subjected to further purification steps if necessary. For example, it may take one or more of deoxidation, decolorization or deodorization processes, but is not limited thereto.
According to the process for preparing the alcohol-free alcohol ester of the present invention, the yield of the alcohol-free alcohol ester can be 70-99%, more specifically 75-95%, and more particularly 80-90% have.
According to another aspect of the present invention, there is provided an anhydrosugar alcohol ester produced by the above method.
The alcohol-free alcohol esters prepared according to the present invention may be a mixture of alcohol-free alcohol mono-esters and di-esters, wherein the sum of the mono-and di-esters is 60 To 85% by weight, and the content of the di-ester may be 45% to 80% by weight.
In addition, the alcohol-free alcohol ester produced according to the present invention may contain not more than 30% by weight of a polymeric ester (for example, a substance in which at least three molecules of carboxylic acid are bonded to a sugar alcohol, an alum alcohol or an imidazole alcohol) , 1 to 30% by weight).
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 that can be added to produce a resin processed product, and the resin processing additive including the alcohol-free alcohol ester may be, 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>
The purity of the prepared alcohol-free alcohol esters was analyzed by 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.
≪ Evaluation of physical properties &
PVC film was prepared by mixing the prepared alcohol - free alcohol ester with polyvinyl chloride (PVC) resin, and Shore A hardness, tensile strength and elongation were evaluated. The evaluation was carried out in comparison with a general plasticizer dioctyl phthalate (DOP).
Example 1
2.3 kg of sorbitol was fed into 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 reactor temperature was raised to 120 ~ 130 ° C to completely melt the sorbitol. While the mixture was maintained after the melting reactor temperature to 70 ~ 90 ℃ supply a sulfuric acid (H 2 SO 4) 0.02kg ( Sorbitol than 1 wt%), and maintain the internal pressure at 90 torr, the internal temperature reaches 120 ~ 140 ℃ It was gradually warmed until it reached. At this time, the internal pressure was lowered to 40 torr, and as a reaction progressed, the generated water was collected through the cooler. After 0.5 to 1 hour reaction, the temperature was lowered to 70 ° C (first stage reaction). The purity measured by the gas chromatography method was 0 to 5% of isosorbide (ISB), 60 to 70% of sorbitan and 0 to 20% of sorbitol.
5.5 kg of 1-octanoic acid (3 equivalents relative to sorbitol) was fed into the reactor. 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, water generated as the reaction progressed was collected through a cooler, and after 30 minutes from the start of the reaction, the internal pressure was gradually lowered to 20 torr or less, and water was removed from the reaction solution as much as possible to complete the reaction (two-step reaction).
The solid content of the reaction solution (hereinafter referred to as " pre-purification reaction solution ") was 95 wt% and the water content was 5 wt%.
The composition (area ratio,%) of the reaction solution before purification was analyzed by a gas chromatograph method, and the results are shown in Table 1. Polymeric ester means a substance in which three or more molecules of carboxylic acid are bonded in the reaction of an intermediate product of a sorbitol dehydration reaction with a carboxylic acid.
After completion of the reaction, the reaction solution was cooled to 70 DEG C while keeping contact with air at a maximum. To the cooled reaction solution was added an aqueous solution diluted with 2 equivalents of 0.8 equivalent of NaOH to 2% sulfuric acid, stirred for several minutes, allowed to stand to separate layers, the aqueous layer was separated, and the organic layer was concentrated to remove residual water. The resulting salt was removed by filtration. The purity measured by the gas chromatograph method was 40 to 50% of the diester of ISB, 0 to 6% of the monoester of ISB, 15 to 20% of the polymeric ester, and 20 to 25% of 1-octanoic acid.
The neutralized reaction was distilled in a short path distillation (SPD) to separate 1-octanoic acid from the ester of ISB. The temperature of the evaporator is 140 ~ 160ºC. The temperature of the condenser is 40 ~ 60ºC. The operating temperature of the SPD is 25 ~ 30ºC. The speed of the gear pump is 9 ~ 12Hz , blade rotation speed was 50 ~ 150 RPM.
NaCl aqueous solution containing 5 wt% NaOH was added to the distillation result, and the mixture was stirred for 30 minutes, and the mixture was allowed to separate and the aqueous layer was separated. Thereafter, an aqueous NaCl solution containing 0.5 wt% of NaHCO 3 was added, stirred for 30 minutes, and then allowed to stand for separation, and the water layer was separated and washed three times. After the last wash, the organic layer was concentrated to remove residual moisture. The resulting salt was removed by filtration. Purity analysis of the product was carried out by the above gas chromatography method. The composition of the product was 60 to 65% of diester of ISB, 0 to 6% of monoester of ISB, 20 to 30% of polymeric ester, and yield of 90%. Separated 1-octanoic acid was recovered and used as a raw material in the next reaction, and its purity was 90 to 95%.
Example 2
4.3 kg of 1-octanoic acid and 1.0 to 1.9 kg of 1-octanoic acid separated and recovered by SPD in the previous reaction were added to the reactor in the same manner as in Example 1, (The total amount of 1-octanoic acid was equivalent to 3 equivalents to sorbitol). The re-use of 1-octanoic acid was carried out three times in total (Recycle 1 to 3). The average yield of the product was 90%, and even when the recovered carboxylic acid was reused, product purity and yield remained at the same level.
The results of Examples 1 and 2 are summarized in Table 1.
Comparative Example: Esterification reaction of isosorbide finished product with octanoic acid
73 g of isosorbide (ISB, purity 99.9% / solid powder type), 140.5 g (1.95 eq.) Of 1-octanoic acid and 3.6 g (5 wt.% Relative to ISB) of p-toluenesulfonic acid monohydrate, Was fed to a batch reactor connected to a condenser and a collector. 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, when the generated water is collected through the cooler and the generated water becomes 80% or more of the theoretical value, the internal pressure is gradually lowered to 20 torr or lower, It was completed.
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 was performed by the above method. The purity measured by the gas chromatograph method was 92.3% of the diester of ISB and 7.2% of the monobasic ester of ISB, and the yield was 89%.
Physical properties were evaluated using a film prepared by mixing 50 parts by weight of an alcohol-free alcohol ester prepared in Example 1 and 100 parts by weight of a polyvinyl chloride resin and 4 parts by weight of a stabilizer. The results are shown in Table 2 below. Respectively. In the evaluation items, all of the examples and comparative examples showed similar results to dioctyl phthalate (DOP), which is a general plasticizer.
Claims (19)
(2) synthesizing an alcohol-free alcohol ester by esterifying an intermediate product of the reaction for producing an alcohol-free alcohol obtained in the step (1) above with an excess of carboxylic acid;
(3) neutralizing a mixture comprising the alcohol-free alcohol ester and the unreacted carboxylic acid obtained as a result of the step (2), with a basic substance; And
(4) distilling the neutralized mixture containing the alcohol-free alcohol ester and unreacted carboxylic acid obtained as a result of the step (3) and recovering unreacted carboxylic acid therefrom;
≪ / RTI >
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101982124B1 (en) * | 2018-05-10 | 2019-05-24 | 주식회사 삼양사 | Polycarbonate block copolymer composition comprising a bio-based ester composition |
| KR102161123B1 (en) * | 2019-07-09 | 2020-10-05 | 주식회사 삼양사 | Anhydrodugar alcohol-based composition crosslinked with aromatic ether-based epoxy compound and polyol composition prepared by adding alkylene oxide thereto |
| KR102161127B1 (en) * | 2019-07-12 | 2020-10-05 | 주식회사 삼양사 | Anhydrodugar alcohol-alkylene glycol composition and hardener for epoxy resin comprising the same, and epoxy resin composition comprising the hardener |
| KR102161451B1 (en) * | 2019-07-12 | 2020-10-06 | 주식회사 삼양사 | Anhydrous alcohol-based urethane-modified polyol composition and toughening agent for an epoxy resin comprising the same, and epoxy resin composition comprising the toughening agent |
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2015
- 2015-12-11 KR KR1020150176803A patent/KR20170070313A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101982124B1 (en) * | 2018-05-10 | 2019-05-24 | 주식회사 삼양사 | Polycarbonate block copolymer composition comprising a bio-based ester composition |
| KR102161123B1 (en) * | 2019-07-09 | 2020-10-05 | 주식회사 삼양사 | Anhydrodugar alcohol-based composition crosslinked with aromatic ether-based epoxy compound and polyol composition prepared by adding alkylene oxide thereto |
| KR102161127B1 (en) * | 2019-07-12 | 2020-10-05 | 주식회사 삼양사 | Anhydrodugar alcohol-alkylene glycol composition and hardener for epoxy resin comprising the same, and epoxy resin composition comprising the hardener |
| KR102161451B1 (en) * | 2019-07-12 | 2020-10-06 | 주식회사 삼양사 | Anhydrous alcohol-based urethane-modified polyol composition and toughening agent for an epoxy resin comprising the same, and epoxy resin composition comprising the toughening agent |
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