KR20170016227A

KR20170016227A - Synthesis method of dibutyl adipate

Info

Publication number: KR20170016227A
Application number: KR1020150109703A
Authority: KR
Inventors: 홍채환; 여인웅; 이종국
Original assignee: 현대자동차주식회사
Priority date: 2015-08-03
Filing date: 2015-08-03
Publication date: 2017-02-13

Abstract

TECHNICAL FIELD The present invention relates to a technique for producing dibutyl adipate from a bio-derived material which can be industrially used as a plasticizer and cosmetic raw material, an automobile interior surface treatment material. More specifically, the present invention relates to a method for preparing dibutyl adipate after preparing mucic acid from a marine resource galactose, followed by an additional several steps of synthesis.
The present invention proposes a method for producing a new material which can be used as a plasticizer material by utilizing non-food resources. The produced material is used as an industrial chemical material (such as a plastic material for PVC, a raw material for a bonding agent, etc.) Which has the advantage of environmental low load in global oligopoly.

Description

Synthesis method of dibutyl adipate < RTI ID = 0.0 >

The present invention relates to a process for the synthesis of dibutyl adipate from biosugars derived from biomass resources such as marine resources. Specifically, galactose obtained from marine resources, specifically, marine plant resources is used to induce an oxidation reaction to synthesize muconic acid, and then dibutyl muconate is synthesized using the supported rhenium catalyst and acidic substance, And then producing dibutyl adipate through a hydrogenation reaction step and a separation step. Particularly, the method according to the present invention is a synthesis method in which a side reaction does not occur during the reaction and the synthesis material can be easily separated and purified. Furthermore, the material prepared according to the above method is characterized by being used as a plasticizer for petrochemical materials used for surface treatment materials for automobile interior materials, and the like, and the additive material can also be synthesized from a bio-derived material. It is environmentally friendly.

Due to the continued population growth and industrial development, it is clear that petroleum resources are the most dependable resource for humanity, accounting for approximately 95% of the compounds currently produced. However, in the face of the finite amount of reserves and the environmental problems necessarily caused by the use, it is in urgent need to prepare alternatives. Therefore, various alternatives for this purpose have been studied. Among them, biomass derived from plant resources, which are repeatedly produced every year in nature such as corn, sugar cane, woody plant resources, palm and seaweed, Which is an important resource to replace petroleum resources.

The importance of biomass research and development, which can be regarded as a futuristic resource in terms of automobile parts and materials industry, is closely emphasized in the same context. It is true that the bio-materials business is still small and the economic efficiency is lower than that of petrochemical materials. However, recent reports from Utrecht University of the Netherlands with the request of European Bio Plastic Association and EPNOE (European Polysaccharide Network of Excellence) Predicts that the use of biomaterials will surge in the next 10 years, and specifically predicts marketability to replace up to 90% of petroleum extraction materials.

Currently, automobile interior and exterior injection parts are made of polypropylene, nylon, polycarbonate, and acrylonitrile butadiene styrene (ABS). Of these, polypropylene is the most widely used, followed by nylon (about 15 kg per car). Therefore, if the manufacturing technology of such highly utilized resin is converted into a biomass-based one, a considerable ripple effect can be expected. Actually, researches on biomass-based nylon materials are actively underway.

At the same time, studies on the production of bio-derived chemicals are being actively carried out. Particularly, as a specific example, artificial leather materials such as artificial leather applied to automobile interior materials are made of polyvinyl chloride materials. Feature. Currently, all of the plasticizers are manufactured by petrochemical methods, and problems such as infant skin diseases caused by plasticizer elution are continuously being raised.

Under these circumstances, the present inventors have continuously studied a method for easily synthesizing dibutyl adipate with galactose, a bio-sugar derived from marine resources, as a starting material in order to synthesize such new bio-derived plasticizer. As a result, in the case of synthesizing muconic acid through the oxidation reaction of the above-mentioned galactose, adding the supported rhenium catalyst and the acidic substance to synthesize dibutyl muconate, and then subjecting it to a hydrogenation reaction, It has been found that dibutyl muconate can be produced using resources, which are environmentally friendly, economical and highly manufacturable.

In order to solve the problems as described above, the present invention relates to a process for producing galactooligosaccharides by oxidizing galactose derived from biomass to synthesize muconic acid, and then catalytic reduction reaction using a rhenium oxide catalyst and an acidic substance carried on the carrier to produce dibutyl muconate And then separating the dibutyl adipate after the hydrogenation reaction, thereby producing dibutyl adipate efficiently.

In one aspect, the present invention is directed to a process for preparing a dibutyl adipate comprising the steps of:

1) oxidizing galactose, a starting material, to produce muconic acid;

2) reacting in a reaction solvent with a rhenium oxide catalyst supported on the mucic acid prepared in step 1) and an acidic substance to prepare dibutyl muconate; And

3) hydrogenating the dibutyl muconate produced in step 2), and separating the resulting dibutyl adipate.

Hereinafter, the manufacturing method according to the present invention will be described in detail for each step.

In step 1) of the production method according to the present invention, galactose is used as a starting material, and then nitric acid is used for an oxidation reaction to produce muconic acid.

The galactose used as the starting material in step 1) may be various biomass feedstocks, for example plant biomass or marine biomass, but preferably galactose obtained from the marine biomass by the saccharification process is used as the starting material Is used.

Next, in step 2) of the production process according to the present invention, the muconic acid prepared in the step 1) is catalytically reacted with a rhenium catalyst supported on a carrier and an acidic substance in a reaction solvent to prepare dibutyl muconate .

In the step 2), two hydroxy groups of muconic acid produced by the oxidation reaction of galactose are deoxidized and dehydrated by the deoxidation and dehydration reaction in the step 1), thereby forming a double bond while removing two hydroxyl groups. The muconic acid is introduced into a reactor containing a reaction solvent, and then the rhenium catalyst and the acidic substance supported on the carrier are introduced into the reactor to be reacted.

The reactant, muconic acid, is characterized by having an input concentration (mu x acid / reaction solvent) in the range of 1/40 to 1/10 g / cc in comparison with the reaction solvent. When the concentration is less than 1/40, the concentration of the reactant is low and the economical efficiency is deteriorated. When the concentration exceeds 1/10, side reaction occurs.

The supported rhenium catalyst is characterized by using alumina (Al ₂ O ₃ ), silica, or silica silica-alumina as a support, and preferably alumina can be used. The rhenium precursor used in the support is characterized by being a precursor of perrhenic acid and similar chemical structures. In the supporting process, the rhenium metal is contained in the final supported catalyst at a level of 10 to 50%. In one specific embodiment, the precursor solution is introduced into the carrier by an incipient-wetness impregnation method , Followed by drying at room temperature, followed by baking at 500 ° C in an electric furnace for about 5 hours.

As the rhenium catalyst supported on the support, rhenium oxide is preferable. The content of the supported rhenium catalyst to be added to the reaction is in the range of 1/2 to 1/20 of the weight of the muesic acid (catalyst / muesic acid). Outside the above range, the reactivity is lowered and by-products are generated.

Further, in step 2), the acidic substance used together with the rhenium catalyst acts on the hydroxyl group of muesic acid to promote the dehydration reaction. As such acidic substance, various organic acids can be used without limitation, Lt; RTI ID = 0.0 > para-toluenesulfonic < / RTI > Preferably, the content of the acidic substance may be 1/20 to 1/5 of the weight of the catalyst (acidic substance / catalyst).

Further, regarding the reaction conditions of the step 2), dibutyl muconate is produced by using the catalyst and the acidic components in a reaction solvent at a reaction temperature of 125 to 145 캜 and a reaction time of 12 to 36 hours. If the temperature and the time range are out of the above range, there is a disadvantage that economical efficiency of production is deteriorated.

When the reaction step is completed, a reaction solvent such as butanol and a catalyst, a dibutyl muconate component, are present in the reactor. In the step 3) of the production method according to the present invention, the hydrogenation reaction is carried out by continuously feeding the supported noble metal catalyst into the reactor used in the step 2) while flowing the hydrogen gas into the reactor, And separating the resulting dibutyl adipate to prepare dibutyl adipate.

As the supported noble metal catalyst used in step 3), for example, platinum supported on carbon or alumina in an amount of 5 to 10%, or palladium catalyst supported on carbon or alumina in an amount of 5 to 10% can be used, And is 1/10 to 1/2 as a weight ratio of (catalyst / muesic acid) to the input amount of the acid.

Further, the input pressure of the hydrogen gas charged for the hydrogenation reaction is preferably 1 to 50 bar. The above ranges are appropriate since the reactivity is deteriorated when the amount is exceeded, the amount of the feed, and the pressure range are exceeded. Meanwhile, the hydrogenation reaction may be performed for 12 to 24 hours.

Dibutyl adipate is finally prepared through the above-mentioned several steps. By the method of the present invention, dibutyl adipate can be very easily prepared and non-food marine resources can be utilized It is environmentally friendly.

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited by the following examples.

According to the production method of the present invention, dibutyl adipate can be synthesized very easily from galactose through mucolytic acid and dibutyl muconate, and in particular, a polyvinyl chloride material used as a material for automobile parts It is used as a plasticizer material and has very high industrial utilization.

In addition, it has the effect of being an important core technology that can ultimately manufacture environmentally low-load biochemical materials at low cost as a method of utilizing non-food marine resources.

Fig. 1 is a schematic diagram showing synthesis of dibutyl adipate according to the present invention.

Example One

When mucolytic acid prepared from galactose is added into the reactor, the concentration is 1/10 g / cc to the butanol solvent. The reactor was charged with rhenium oxide (rhenium content 25%) catalyst supported on alumina at a ratio of 1/10 of the weight of muesic acid. Further, paratoluene sulfonic acid was added at a ratio of 1/10 with respect to the weight of the above-introduced catalyst.

Thereafter, the mixture was maintained at 125 DEG C for 24 hours, and palladium catalyst supported on alumina was added at a ratio of 1/10 of the weight of muesic acid. The reactor temperature was maintained at room temperature, and hydrogen gas was introduced into the reactor to maintain the pressure at 10 bar. After 24 hours of reaction time, the desired reaction product, namely dibutyl adipate, was recovered and the melting point and the boiling point were measured to determine whether the material was synthesized.

Example 2 to 4

Dibutyl adipate was prepared in the same manner as in Example 1 except that the amounts and conditions of the materials participating in the reaction were changed as shown in Table 1 below.

Comparative Example One

The same production method as in Example 1 is used except that the amount and condition of the materials participating in the reaction are different from the scope of the present invention. The detailed conditions are shown in Table 1 below.

division Example conditions
(Ratio, temperature, weight%) Comparative Example Condition
(Ratio, temperature, weight%) One 2 3 4 One 2 3 4 (A) 1/10 1/20 1/30 1/40 1/5 1/3 1/2 1/1 (B) 1/20 1/10 1/5 1/2 1/1 1/1 1/1 1/1 (C) 1/10 1/10 1/10 1/10 1/10 1/10 1/10 1/10 (D) 1/10 1/7 1/5 1/2 1/30 1/40 1/50 1/60 (E) 125 130 135 140 110 105 100 95 (F) 10 bar / 12 hr 10 bar / 24 hr 10 bar / 36 hr 10 bar / 48 hr 1 bar / 12 hr 1 bar / 24 hr 1 bar / 36 hr 1 bar / 48 hr (G) -38 ^o C -38 ^o C -38 ^o C -38 ^o C Not measured Not measured Not measured Not measured Synthesis result o o o o X X X X Synthesis condition Component Condition (A): [mu] acid (material name); Direct production by Hyundai Motor] Input ratio (mu acid / butanol)
Component condition (B): [supported rhenium oxide catalyst; Hyundai Motor's direct manufacturing)] Input ratio (catalyst / mu-acids)
Component condition (C): Paratoluenesulfonic acid (Sigma Aldrich, USA) Feed ratio (para-toluenesulfonic acid / catalyst)
Component condition (D): Alumina-supported palladium catalyst [Sigma Aldrich, USA] Feed ratio (catalyst / muesic acid)
Component condition (E): reaction temperature (dibutyl muconate synthesis temperature from mu acid)
Reaction condition (F): Hydrogen pressure and supply holding time
Synthesis result (G): Melting point measurement

Test Example : Melting point and boiling point measurement

The melting point and boiling point of the samples prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured. Melting point measurement was performed by staying the sample in a cryogenic freezer at -70 ° C or less, taking out the sample, and measuring the melting point using an automatic melting point measuring device. The boiling point was measured by the OECD TG 103 method.

As shown in Table 1, in the case of Examples 1 to 4 of the present invention prepared under specific reaction conditions (reaction temperature and catalyst content, etc.) of the present invention, unlike Comparative Examples 1 to 4 deviating from specific conditions, Dibutyl adipate was synthesized.

Claims

A process for preparing a dibutyl adipate comprising the steps of:
1) oxidizing galactose, a starting material, to produce muconic acid;
2) reacting in a reaction solvent with a rhenium oxide catalyst supported on the mucic acid prepared in step 1) and an acidic substance to prepare dibutyl muconate; And
3) hydrogenating the dibutyl muconate produced in step 2), and separating the resulting dibutyl adipate.

The method according to claim 1,
Wherein the starting material, galactose, is produced from a marine biomass by a glycosylation process.

The method according to claim 1,
Wherein in said step 1), galactose is oxidized using nitric acid to produce muesic acid.

The method according to claim 1,
Wherein the added concentration of the muesic acid to the reaction solvent in the step 2) is 1/40 to 1/10 g / cc.

The method according to claim 1,
Wherein the supported rhenium oxide catalyst of step 2) comprises a carrier selected from the group consisting of alumina, silica and silica silica-alumina as the support.

6. The method of claim 5,
Wherein the content of rhenium supported on the support is 10 to 50%.

The method according to claim 1,
Wherein the supported rhenium oxide catalyst content is 1/2 to 1/20 by weight relative to the muesic acid.

The method according to claim 1,
Wherein the acidic substance of step 2) is para-toluenesulfonic acid.

The method according to claim 1,
Wherein the content of the acidic substance in the step 2) is 1/20 to 1/5 of the weight of the catalyst.

The method according to claim 1,
Wherein the step 2) is carried out at a reaction temperature of 125 to 145 캜 for a reaction time of 12 to 36 hours.

The method according to claim 1,
Wherein the reaction solvent is butanol.

The method according to claim 1,
After completion of step 2), step 3) is carried out continuously in the same reactor.

13. The method of claim 12,
Wherein a noble metal catalyst loaded for hydrogenation reaction is introduced and hydrogen gas is flowed into the reactor.

14. The method according to claim 13, wherein the supported noble metal catalyst is palladium catalyst supported on carbon or alumina in an amount of 5 to 10%, or supported on carbon or alumina in 5 to 10%.

14. The production method according to claim 13, wherein the amount of the supported noble metal catalyst is 1/10 to 1/2 of the weight of muesic acid.

14. The method of claim 13,
Wherein the hydrogen gas is introduced at a pressure of 1 to 50 bar.

14. The method of claim 13,
Wherein the hydrogenation reaction is conducted for 12 to 24 hours.