KR20190111219A - Method for preparing furan dialkylcarboxylate using galactaric acid - Google Patents

Abstract

The present invention relates to a furan dialkylcarboxylate producing method which includes a step of producing a compound represented by a structural formula 1 and/or a compound represented by a structural formula 2 by making galactaric acid react with alcohol while removing water in the presence of an acid catalyst and a material separation agent as shown in a reaction formula 1. The method for producing furan dialkylcarboxylate of the present invention is able to obtain furan dialkylcarboxylate in an excellent yield through a single reaction from galactic acid; and the furan dialkylcarboxylate produced by the furan dialkylcarboxylate producing method is able to replace existing phthalate plasticizer such as dioctyl phthalate (DOP).

Description

Method for producing furan dialkyl carboxylate using galactic acid {METHOD FOR PREPARING FURAN DIALKYLCARBOXYLATE USING GALACTARIC ACID}

The present invention relates to a method for producing a furan dialkyl carboxylate, and more particularly, a method for producing a furan dialkyl carboxylate which can obtain a furan dialkyl carboxylate in a good yield from a galactic acid through a single reaction. It is about.

Polymer resins have been used in various fields, such as living and home appliances, clothing, automobiles, construction materials or packaging materials according to their characteristics. To date, plastic resins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polyurethane (PU), and polyvinyl chloride (PVC) are widely used. In particular, PVC resin is hard, soft properties and various molding is possible, and excellent price competitiveness has been applied to a variety of applications from household goods to industrial materials with a universal utility.

Rather than using PVC resin alone, plasticizers are added to implement various physical properties. The plasticizer serves to impart flexibility of the PVC resin to improve processability and applicability. However, with the development of the industry, the role of plasticizers has been diversified, and not only flexibility but also the characteristics required by the application fields such as volatility, migration resistance, aging resistance, cold resistance, oil resistance, water resistance, heat resistance, etc.

Plasticizers to vinyl chloride resins include polyester plasticizers, epoxidized vegetable oil plasticizers such as epoxidized soybean oil (ESBO), phthalate ester plasticizers such as dioctyl phthalate (DOP) and diisononyl phthalate (DINP), and adipic. Many plasticizers, such as adipic acid type plasticizers, such as an acid dioctyl (DOA) and adipic acid diisononyl (DINA), and trimellitic acid type plasticizers, such as trimellitic acid trioctyl (TOTM), are used.

Di (ethylhexyl) phthlate (DOP), which belongs to the family of phthalate ester plasticizers in the world market, is the most common and commercially used. DOP dominates the market, accounting for about 90% of the products produced annually, due to their low production costs and their high capacity for their polymer matrix. However, DOP is an organic chemical manufactured from petroleum, which is toxic to living organisms and has a problem that is not environmentally friendly. Therefore, it is urgent to develop eco-friendly plasticizer to replace it.

An object of the present invention is to solve the above problems, to provide a method for producing a furan dialkyl carboxylate can be obtained in a good yield of furan dialkyl carboxylate from a galactic acid through a single reaction.

In addition, the present invention provides a method for preparing a furan dialkyl carboxylate that can replace a conventional phthalate plasticizer such as DOP (dioctyl phthalate).

According to an aspect of the present invention, by reacting the galactaric acid with an alcohol while removing water in the presence of an acid catalyst and a material separation agent as shown in Scheme 1 and / or Formula 2 Provided is a method for preparing furanedialkyl carboxylate comprising the step of preparing a compound represented by.

 Scheme 1

In Scheme 1, R is C1-C10 straight chain alkyl group or C3-C10 ground alkyl group.

The method for preparing furanedialkyl carboxylate is (a) preparing a mixed solution by adding the galactaric acid, an alcohol, an acid catalyst and a separating agent; And (b) reacting the mixed solution with the galactaric acid and the alcohol while removing water to prepare a compound represented by Formula 1 and / or a compound represented by Formula 2. have.

Step (b) may be carried out at a temperature of 70 to 200 ℃.

Step (b) may be carried out at a temperature of 100 to 170 ℃ of the mixed solution.

In step (b), an esterification reaction may be performed.

The galactic acid may be obtained from galactose.

Alcohol having a linear or pulverized alkyl group consisting of 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, isopentanol, isobutanol and the like It may include one or more selected from.

The catalyst may include at least one selected from inorganic acids consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like, and organic acids including functional groups such as sulfonic acid (-SO ₃ H) and carboxylic acid (-CO ₂ H). .

The catalyst may be sulfuric acid.

The separating agent is selected from an aromatic hydrocarbon compound consisting of benzene, toluene, o-xylene, m-xylene, p-xylene and the like and a C6-C16 aliphatic hydrocarbon compound consisting of hexane, heptane, octane, decane, dodecane and the like. It may include one or more.

The separating agent may be p-xylene.

The compound represented by Formula 1 or 2 may be any one selected from the following Structural Formulas 3 to 6.

The compound represented by Formula 1 or 2 may be a compound represented by Formula 6.

According to another aspect of the invention, a plasticizer comprising a compound represented by the formula 1 or 2 below; And a thermoplastic polymer is provided.

[Formula 1]

[Formula 2]

In the above formula 1 and 2,

Each R is independently a C1-C10 straight chain alkyl group or a C3-C10 ground chain alkyl group.

The polymer chains such as polyvinyl chloride, polyethylene, polypropylene, polybinyl alcohol, polyalkyl methacrylate, polyvinylbutyral, etc. Polymeric polymers, polylactic acid, polyhydroxybutyral, polyester, polycarbonate, polyamide, polyurea, polyurethane, etc. It may include one or more selected from condensation polymers of.

The polymer may include polyvinyl chloride.

The method for producing the furan dialkyl carboxylate of the present invention can obtain a furan dialkyl carboxylate in excellent yield through a single reaction from galactic acid.

In addition, the furan dialkyl carboxylate prepared according to the method for producing a furan dialkyl carboxylate may replace the existing phthalate plasticizer such as DOP (dioctyl phthalate).

1 is a schematic view of a furan dialkylcarboxylate production method of the present invention.
2A and 2B show the results of ¹ H-NMR and ¹³ C-NMR analysis of Examples 1-1, 1-2, 2-1, and 2-2.
3A to 3D show FT-IR analysis results of Examples 1-1, 1-2, 2-1, and 2-2.
4 shows the results of mass spectrometry (EI-MS +) spectra of Examples 1-1, 1-2, 2-1, and 2-2.
5A to 5E show FE-SEM images of Examples 3-1, 3-2, 4-1, and 4-2 and Comparative Example 2. FIG.
6 is a graph showing the change in glass transition temperature according to the plasticizer content.
FIG. 7A is a graph showing a change in elastic modulus (E-Modulus) according to the type of plasticizer, FIG. 7B is a graph showing a change in stress at break according to the type of plasticizer, and FIG. 7C is a breakage time according to the type of plasticizer. It is a graph showing the change in elongation at break.
8 is a thermogravimetric analysis (TGA) curve of Examples 3-1, 3-2, 4-1 and 4-2.
9 is a graph comparing the volatility of the plasticizer according to Examples 1-1, 1-2, 2-1 and 2-2 and Comparative Example 1. FIG.
10 is a graph comparing the amounts of the plasticizers according to Examples 1-1, 1-2, 2-1 and 2-2 and Comparative Example 1, which were discharged in hot hexane for 2 hours.

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

However, the following description is not intended to limit the present invention to specific embodiments, and it should be understood that the present invention covers all the transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, operation, component, or combination thereof described in the specification, and one or more other features or It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, operations, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later. As used herein, unless otherwise defined, the term "alkyl group" means a straight chain, pulverized or cyclic aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" containing at least one double or triple bond.

The alkyl group may be a C1 to C14 alkyl group. More specifically, it may be a C1 to C10 alkyl group or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:

Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl and cyclo A butyl group, a cyclopentyl group, a cyclohexyl group, etc. are meant.

1 is a schematic view of a furan dialkylcarboxylate production method of the present invention.

Hereinafter, a method for preparing furan dialkyl carboxylate will be described in detail with reference to FIG. 1.

The present invention reacts the compound represented by formula 1 and / or the compound represented by formula 2 by reacting galactaric acid with alcohol while removing water in the presence of an acid catalyst and a material separation agent, as shown in Scheme 1. It provides a method for producing a furanedialkyl carboxylate comprising the step of preparing.

Scheme 1

In Scheme 1, R is C1-C10 straight chain alkyl group or C3-C10 ground alkyl group.

Here the material separation agent can remove the azeotrope of alcohol / water in order to change the interaction of molecules and to remove water effectively. This has the advantage of increasing the yield of furandialkylcarboxylate under the same reaction conditions compared to when no separation agent is used. In addition, it is possible to maximize the yield of the furandialkyl carboxylate by controlling the amount of the separating agent.

The method for preparing furanedialkyl carboxylate is (a) preparing a mixed solution by adding the galactaric acid, an alcohol, an acid catalyst and a separating agent; And (b) reacting the mixed solution with the galactaric acid and the alcohol while removing water to prepare a compound represented by Formula 1 and / or a compound represented by Formula 2. have.

Step (b) may be carried out at a temperature of 70 to 200 ℃.

Step (b) may be carried out at a temperature of 100 to 170 ℃ of the mixed solution.

In step (b), an esterification reaction may be performed.

The galactic acid may be obtained from galactose.

The alcohol may include one or more selected from alcohols having a linear or pulverized alkyl group, preferably 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, Isopentanol, isobutanol.

The catalyst may include one or more selected from inorganic and organic acids, the inorganic acid may be sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like, and the organic acid may be sulfonic acid (-SO ₃ H), carboxylic acid (-CO _It may be an organic acid containing a functional group such as ₂ H), preferably sulfuric acid.

The separating agent may include at least one selected from an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound of C 6 -C 16, wherein the aromatic hydrocarbon compound is benzene, toluene, o-xylene, m-xylene, p-xylene, or the like. The C6-C16 aliphatic hydrocarbon compound may be hexane, heptane, octane, decane, dodecane, or the like, and preferably, may be p-xylene.

The compound represented by Formula 1 or 2 may be any one selected from the following Structural Formulas 3 to 6.

The compound represented by Formula 1 or 2 may be a compound represented by Formula 6.

According to another aspect of the present invention, a plasticizer comprising a compound represented by the formula 1 or 2 below; And a thermoplastic polymer is provided.

[Formula 1]

[Formula 2]

In the above formula 1 and 2,

Each R is independently a C1-C10 straight chain alkyl group or a C3-C10 ground chain alkyl group.

The polymer is made of polyvinyl chloride, polyethylene, polypropylene, polybinyl alcohol, polyalkyl methacrylate, polyvinylbutyral, and the like. Chain Polymers and Polylactic Acid, Polyhydroxybutyral, Polyester, Polycarbonate, Polyamide, Polyurea, Polyurethane It may include one or more selected from condensation polymers consisting of, and the like, preferably polyvinyl chloride.

EXAMPLE

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes and the scope of the present invention is not limited thereby.

The chemicals used in the following examples are as follows, and the names are abbreviated in parentheses.

1-butanol (BuOH, over 99.5%), galactic acid (Gal-dA, 97%; also known as benzoic acid), 3-methyl-1-butanol (iAmOH, 98%, commonly known as isoamyl alcohol) , Sodium carbonate (Na ₂ CO ₃ , anhydrous, over 99.5%), sodium chloride (NaCl, anhydrous, 99%), sulfuric acid 98% fume (H ₂ SO ₄ ), p-xylene (99%) are all Sigma- It was purchased from Aldrich (Korea) and used directly without purification. Molecular sieves type 3mm3 (UOP, pellets, 3.2 mm) purchased from Sigma-Aldrich (USA) was dried at 220 ° C prior to use. Samchun Chemicals Co. Ltd. Analytical solvents (n-hexane, ethyl acetate, methanol) purchased from (Korea) were dried in molecular sieves 3Å prior to use. Tetrahydrofuran (THF, anhydrous and inhibitor-free,> 99.9%), polyvinyl chloride (PVC, number average molecular weight ~ 80,000, weight average molecular weight ~ 47,000), and activated carbon (4-14 mesh) are all Sigma-Aldrich (USA) ) Was used immediately without purification.

Example 1: Preparation of Di-n-butyl Furancarboxylates (DBFs)

Example  1-1 and 1-2: di -n-butyl furan -2,5- carboxylate  (p- DBF ) And di -n-butyl furan -2,3- carboxylate  (o- DBF )

Galactic acid (Gal-dA, 5.0 gr, 23.79 mmol) was suspended in 50 mL of 1-butanol in a Dean-Stark apparatus. The suspension was heated at the boiling point of 1-butanol and sulfuric acid (2.0 gr) and p-xylene were added dropwise. The temperature was then raised to and maintained at 160 ° C. After 10 hours, the reaction mixture was cooled, diluted with ethyl acetate (EtOAc) and washed with a saturated solution of NaCl and an aqueous solution of Na ₂ CO ₃ (10%, w / w). The organic phase was dried in molecular sieve and evaporated under reduced pressure. The product was purified by flash chromatography simultaneously on silica gel (60 μs, 230-400 mesh) of Sigma-Aldrich (USA) under UV lamps of 245 nm and 265 nm to di-n-butyl furan-2,5-carboxylate (Example 1- 1, p-DBF, 60-65% obtained), di-n-butyl furan-2,3-carboxylate (Example 1-2, o-DBF, 27-32% obtained) were prepared and ¹ H-NMR And ¹³ C-NMR.

The reaction of Example 1 is shown in Scheme 2 shown below.

Scheme 2

Data of ¹ H-NMR and ¹³ C-NMR of p-DBF (Example 1-1) and o-DBF (Example 1-2) prepared according to Example 1 are as follows.

Example 1-1 Di-n-butyl furan-2,5-dicarboxylate (p-DBF)

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.18 (s, 1H), 4.32 (t, J = 6.7 Hz, 2H), 1.79-1.67 (m, 2H), 1.43 (sextet, J = 7.3 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H)

¹³ C-NMR (CDCl ₃ , 75 MHz): δ 158.31, 147.07, 118.30, 65.52, 30.74, 19.21, 13.80

Example 1-2 Di-n-butyl furan-2,3-dicarboxylate (o-DBF)

¹ H-NMR (CDCl ₃ , 300 MHz): δ 6.97 (d, J = 7.5 Hz, 1H), 6.46 (d, J = 7.6 Hz, 1H), 4.07 (t, J = 6.7 Hz, 2H), 3.83 (t, J = 6.5 Hz, 2H), 1.68-1.57 (m, 2H), 1.55-1.45 (m, 2H), 1.35-1.15 (m, 4H), 0.743 (triplet, J = 7.4 Hz, 3H), 0.735 (triplet, J = 7.4 Hz, 3H)

¹³ C-NMR (CDCl ₃ , 75 MHz): δ 158.96, 156.36, 148.44, 140.33, 111.67, 111.08, 69.22, 65.26, 30.15, 30.09, 18.68, 18.67, 13.26, 13.22

Example 2: Preparation of Diisoamyl Furancarboxylates (DIAFs)

Example  2-1 and 2-2: diisoamyl furan -2,5- dicarboxylate  (p- DIAF ) And diisoamyl furan-2,3-carboxylate (o-DIAF)

Galactic acid (Gal-dA, 5.0 gr, 23.79 mmol) was suspended in 50 mL of 3-methyl-1-butanol in a Dean-Stark apparatus. The suspension was heated at the boiling point of 3-methyl-1-butanol and sulfuric acid (1.2 gr) and p-xylene were added dropwise. The temperature was then raised to and maintained at 160 ° C. After 10 hours, the reaction mixture was cooled, diluted with ethyl acetate (EtOAc) and washed with a saturated solution of NaCl and an aqueous solution of Na ₂ CO ₃ (10%, w / w). The organic phase was dried in molecular sieve and evaporated under reduced pressure. The product was purified by flash chromatography simultaneously on silica gel (60 μs, 230-400 mesh) of Sigma-Aldrich (USA) under UV lamps of 245 nm and 265 nm to diisoamyl furan-2,5-carboxylate (Example 2-1, p- DIAF, 55-64% obtained), diisoamyl furan-2,3-carboxylate (Example 2-2, o-DIAF, 30-35% obtained) were prepared and subjected to ¹ H-NMR and ¹³ C-NMR. .

The reaction of Example 2 is shown in Scheme 3, shown below.

Scheme 3

Data of ¹ H-NMR and ¹³ C-NMR of p-DIAF prepared in Example 2 (Example 2-1) and o-DIAF (Example 2-2) are as follows.

Example 2-1 Diisoamyl furan-2,5-dicarboxylate (p-DIAF)

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.18 (s, 1H), 4.35 (t, J = 6.8 Hz, 2H), 1.83-1.58 (m, 3H), 0.95 (d, J = 6.8 Hz, 6H)

¹³ C-NMR (CDCl ₃ , 75 MHz): δ 158.31, 147.07, 118.32, 64.37, 37.37, 25.21, 22.58

Example 2-2: Diisoamyl furan-2,3-dicarboxylate (o-DIAF)

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.08 (d, J = 7.5 Hz, 1H), 6.47 (d, J = 7.6 Hz, 1H), 4.26 (t, J = 6.8 Hz, 2H), 3.97 (t, J = 6.6 Hz, 2H), 1.86-1.63 (m, 4H), 1.63-1.52 (m, 2H), 0.941 (d, J = 6.4 Hz, 6H), 0.932 (d, J = 6.5 Hz, 6H)

¹³ C-NMR (CDCl ₃ , 75 MHz): δ 159.48, 156.71, 148.91, 140.93, 111.72, 111.05, 68.28, 64.63, 37.16, 37.02, 24.99, 24.86, 22.41

Example 3-1 Preparation of Film comprising Example 1-1 as Plasticizer

PVC powder (2.5 g, average Mw-80,000, average Mn-47,000) is a plasticizer of about 55 mL with di-n-butyl furan-2,5-carboxylate (p-DBF) prepared according to Example 1-1. After dissolving in tetrahydrofuran (THF, anhydrous and inhibitor-free, over 99.9%) and stirred for at least 3 hours. The stirred solution was placed in a clean Petri dish. The THF solvent was evaporated overnight and then placed in a vacuum oven at 35 ° C. for 24 hours to produce a flexible film.

Example 3-2 Preparation of Film comprising Example 1-2 as Plasticizer

Di-n-butyl furan prepared according to Example 1-2 as a plasticizer instead of using di-n-butyl furan-2,5-carboxylate (p-DBF) prepared according to Example 1-1 as a plasticizer. A flexible film was prepared in the same manner as in Example 3-1 except for using -2,3-carboxylate (o-DBF).

Example 4-1 Preparation of Film comprising Example 2-1 as Plasticizer

Diisoamyl furan-2,5 prepared according to Example 2-1 as a plasticizer instead of using di-n-butyl furan-2,5-carboxylate (p-DBF) prepared according to Example 1-1 as a plasticizer. A flexible film was prepared in the same manner as in Example 3-1 except for using -carboxylate (p-DIAF).

Example 4-2 Preparation of Film comprising Example 2-2 as Plasticizer

Diisoamyl furan-2,3 prepared according to Example 2-2 as a plasticizer instead of using di-n-butyl furan-2,5-carboxylate (p-DBF) prepared according to Example 1-1 as a plasticizer. A flexible film was prepared in the same manner as in Example 3-1 except for using -carboxylate (o-DIAF).

Comparative Example 1: di (ethylhexyl) phthalate (DOP)

Bis (2-ethylhexyl) phthalate (DOP, over 98%) was purchased from TCI Chemicals (Japan).

Comparative Example 2: Preparation of Film Containing Comparative Example 1 as Plasticizer

Instead of using di-n-butyl furan-2,5-carboxylate (p-DBF) prepared according to Example 1-1 as a plasticizer, bis (2-ethylhexyl) phthalate (DOP) according to Comparative Example 1 as a plasticizer Except for using a flexible film was prepared in the same manner as in Example 3-1.

Comparative Example 3: Preparation of Plasticizer Without Separation Agent

P-DBF (30-33) in the same manner as in Examples 1-1 and 1-2 except that p-xylene is not added dropwise instead of p-xylene in Examples 1-1 and 1-2. %), O-DBF (10-12% obtained) was prepared.

[Test Example]

Test Example 1: NMR Analysis

2A and 2B show the results of ¹ H-NMR and ¹³ C-NMR analysis of Examples 1-1, 1-2, 2-1, and 2-2. NMR analysis was performed using Bruker Spectrospin 300 (Germany) using chloroform-d (CDCl ₃ ) and deuterated tetramethylsilane (TMS, δ = 0 ppm).

NMR of p-DBF (Example 1-1), o-DBF (Example 1-2), p-DIAF (Example 2-1) and o-DIAF (Example 2-2) of FIGS. 2A and 2B The analytical results are shown in Tables 1 to 4 below.

Example 1-1 (p-DBF) Position ¹ H-NMR ¹³ C-NMR Peak J coupling Peak a 0H - 147.07 ppm b 7.18 ppm, s, 1 H - 118.30 ppm e 0H - 158.31 ppm g 4.32 ppm, t, 2 H 6.7 Hz 65.52 ppm h 1.79-1.67 ppm, m, 2H - 30.74 ppm i 1.43 ppm, sextet, 2H 7.3 Hz 19.21 ppm j 0.95 ppm, t, 3H 7.4 Hz 13.80 ppm

Referring to Table 1, the structure of Example 1-1 (p-DBF) di-n-butyl furan-2,5-dicarboxylate (2,5-DBF) has five protons and seven carbons I knew it was.

Example 1-2 (o-DBF) Position ¹ H-NMR ¹³ C-NMR Peak J coupling Peak a 0H - 148.44 ppm b 0H - 111.67 ppm c 6.46 ppm, d, 1 H 7.6 Hz 111.08 ppm d 6.97 ppm, d, 1 H 7.5 Hz 140.33 ppm e 0H - 156.36 ppm f 0H - 158.96 ppm g 3.83 ppm, t, 2H 6.5 Hz 65.26 ppm g ' 4.07 ppm, t, 2 H 6.7 Hz 69.22 ppm h 1.55-1.45, m, 2H - 30.09 ppm h ' 1.68-1.57 ppm, m, 2H - 30.15 ppm i 1.35-1.15 ppm, m, 4H - 18.67 ppm i ' H _i and H _{i 'were} overlapped - 18.68 ppm j 0.735 ppm, t, 3H 7.4 Hz 13.22 ppm j ' 0.743 ppm, t, 3H 7.4 Hz 13.26 ppm

Referring to Table 2, the structure of n-butyl furan-2,3-dicarboxylate (2,3-DBF) which is Example 1-2 (o-DBF) is divided into 10 protons and 14 carbons And some of them overlap with others.

Example 2-1 (p-DIAF) Position ¹ H-NMR ¹³ C-NMR Peak J coupling Peak a 0H - 147.07 ppm b 7.18 ppm, s, 1 H - 118.32 ppm e 0H - 158.31 ppm g 4.35 ppm, t, 2H 6.8 Hz 64.37 ppm h 1.83-1.58 ppm, m, 3H - 37.37 ppm i H _{h i} and H were overlapped - 25.21 ppm j 0.95 ppm, t, 6H 6.8 Hz 22.58 ppm

Referring to Table 3, it can be seen that the structure of Diisoamyl furan-2,5-dicarboxylate (2,5-DIAF), which is Example 2-1 (p-DIAF), has 5 protons and 7 carbons. there was.

Example 2-2 (o-DIAF) Position ¹ H-NMR ¹³ C-NMR Peak J coupling Peak a 0H - 148.91 ppm b 0H - 111.72 ppm c 6.47 ppm, d, 1 H 7.6 Hz 111.05 ppm d 7.08 ppm, d, 1 H 7.5 Hz 140.93 ppm e 0H - 156.71 ppm f 0H - 159.48 ppm g 3.97 ppm, t, 2H 6.6 Hz 64.63 ppm g ' 4.26 ppm, t, 2 H 6.8 Hz 68.28 ppm h 1.63-1.52, m, 2H - 37.02 ppm h ' 1.86-1.63 ppm, m, 4H - 37.16 ppm i _{H h ', H i and H} i' were - 24.86 ppm i ' overlapped - 24.99 ppm j 0.932 ppm, d, 6 H 6.5 Hz 22.41 ppm j ' 0.941 ppm, d, 6H 6.4 Hz C _j and C _{j '} were overlapped

Referring to Table 4, the structure of Diisoamyl furan-2,3-dicarboxylate (2,3-DIAF) of Example 2-2 (o-DIAF) is divided into 10 protons and 14 carbons, Some of them overlapped with others.

Test Example 2: FT-IR Analysis

3A to 3D show FT-IR analysis results of Examples 1-1, 1-2, 2-1, and 2-2. FT-IR analysis was performed using a Nicolet 6700 FT-IR Spectrometer (Thermo Fisher, USA).

FT of p-DBF (Example 1-1), o-DBF (Example 1-2), p-DIAF (Example 2-1) and o-DIAF (Example 2-2) of FIGS. 3A-3D The IR analysis results are shown in Tables 5 to 8 below.

Example 1-1 (p-DBF) Range
(cm ^-1 ) Typical peak (s)
(cm ^-1 ) Vibration type 3180-3090 3155, 3118 C _sp2 -H stretching 3000-2800 2958, 2933, 2872 C _sp3 -H stretching 1820-1640 1726, 1709 C = O, conjugated 1600-1492 1576, 1510 C = C, conj. arom. 1492-1440 1476, 1468 C _sp3 -H bending 1420-1340 1393, 1383, 1372, 1355 C _sp2 -H bending 1340-1080 1281, 1267, 1231, 1151, 1126 C-O stretching 790-750 772 Ar-C, conj. 750-700 735 C _sp2 -H oop, conj.

Example 1-2 (o-DBF) Range
(cm ^-1 ) Typical peak (s)
(cm ^-1 ) Vibration type 3160-3050 3117, 3075 C _sp2 -H stretching 3000-2760 2960, 2937, 2906, 2873 C _sp3 -H stretching 1840-1500 1716, 1557 C = O, conjugated 1660-1430 1637, 1468 C = C, conj. arom. 1500-1425 1474, 1449 C _sp3 -H bending 1420-1330 1387, 1369, 1342, 1335 C _sp2 -H bending 1340-1040 1248, 1138, 1126, 1094 C-O stretching 800-745 760 Ar-C, conj. 745-700 731 C _sp2 -H oop, conj.

Example 2-1 (p-DIAF) Range
(cm ^-1 ) Typical peak (s)
(cm ^-1 ) Vibration type 3200-3080 3161, 3128 C _sp2 -H stretching 3050-2760 2958, 2931, 2907, 2872 C _sp3 -H stretching 1860-1660 1739, 1719 C = O, conjugated 1620-1500 1582, 1530 C = C, conj. arom. 1500-1420 1465, 1432 C _sp3 -H bending 1420-1330 1387, 1369, 1342, 1335 C _sp2 -H bending 1330-1080 1300, 1272, 1222, 1128 C-O stretching 790-720 766 Ar-C, conj.

Example 2-2 (o-DIAF) Range
(cm ^-1 ) Typical peak (s)
(cm ^-1 ) Vibration type 3150-3040 3116, 3084, 3065 C _sp2 -H stretching 3000-2760 2953, 2868 C _sp3 -H stretching 1840-1510 1732, 1713, 1557 C = O, conjugated 1660-1430 1635, 1471 C = C, conj. arom. 1500-1420 1468, 1455 C _sp3 -H bending 1420-1320 1405, 1387, 1367, 1341 C _sp2 -H bending 1320-1010 1252, 1142, 1134, 1091 C-O stretching 780-720 762 Ar-C, conj.

3A to 3D and Tables 5 to 8, p-DBF (Example 1-1), o-DBF (Example 1-2), and p-DIAF (Example 2) by the method according to the embodiment of the present invention. -1) and o-DIAF (Example 2-2) were confirmed to be synthesized.

Test Example 3: Mass Spectrometry Spectrum Analysis

Figure 4 shows the mass spectrometry (EI-MS +) spectrum analysis results of Examples 1-1, 1-2, 2-1 and 2-2. Mass spectrometry was performed using Shimadzu GCMS-QP-2010 Ultra integrated with Shimadzu GC of Mass Spectrometer GC-2010 Plus (Japan).

Referring to FIG. 4, the EI-MS of p-DBF (Example 1-1) is 41.1 (17.40%), 56.2 (55.72%), 139.1 (79.29%), 157.1 (100%), 167.1 (11.19%) , 195.1 (29.72%), 213.1 (10.89%), M ⁺ 268.1 (1.99%), and EI-MS of o-DBF (Examples 1-2) was 41.1 (62.17%), 57.2 (64.13%) , 82.1 (56.54%), 128.1 (46.28%), 139.1 (11.61%), 156.1 (100%), 157.1 (H ⁺ , 33.92%), 167.1 (41.48%), 195.1 (2.42%), 212.1 (14.83% ), M ⁺ 268.1 (5.45%).

In addition, the EI-MS of p-DIAF (Example 2-1) was 41.1 (94.35%), 56.1 (53.56%), 57.1 (73.24%), 69.0 (59.57%), 100.0 (21.16%), 128.0 (13.43) %), 139.0 (100%), 156.0 (35.15%), 157.0 (76.87%), 195.0 (9.70%), 213.0 (13.46%), 268.1 (3.14%) 281.0 (0.08%), M + 296.2: indicated as unfound EI-MS of o-DIAF (Example 2-2) was 41.1 (86.33%), 57.1 (76.77%), 82.0 (70.51%), 128.0 (54.14%), 139.0 (13.85%), 156.0 (100 %), 157.0 (34.53%), 167.0 (52.52%), 212.0 (14.31%), 268.0 (5.53%), 281.0 (0.01%), M + 296.2: unfound.

Test Example 4 Surface Morphology Comparison

5A to 5E show FE-SEM images of Examples 3-1, 3-2, 4-1, and 4-2 and Comparative Example 2. FIG.

According to FIGS. 5A-5E, there is no apparent phase separation between the plasticizers (Examples 1-1, 1-2, 2-1 and 2-2 and Comparative Example 1) and the matrix (PVC) at 1 μm magnification so that there is Compatibility) is good. In addition, when compared with Comparative Example 2 (DOP 50%), Example 3-1 (p-DBF 50%), 3-2 (o-DBF 50%), 4-1 (p-DIAF 50%) and 4 The surface of the film of -2 (o-DIAF 50%) was confirmed to be uniform and flat.

Test Example 6 Comparison of Glass Transition Temperatures

6 is a graph showing the change in glass transition temperature according to the plasticizer content. The results are shown in Table 9 below, and differential scanning calorimetry (DSC) was measured using DSC 8000 (PerkinElmer, USA).

Content
(%) Glass Transition Temperature (° C) Example 3-1 Example 4-1 Example 3-2 Example 4-2 0 80.77 80.77 80.77 80.77 5 59.83 62.44 62.74 66.72 10 51.00 53.25 56.18 58.34 20 29.20 35.13 41.11 44.65 30 20.49 21.40 29.77 33.05 40 7.67 8.46 20.38 21.65 50 -1.53 -2.80 13.01 11.36

According to Figures 6 and 9, Example 3-1 (p-DBF containing film) and Example 4-1 (p-DIAF containing film) increased the amount of plasticizer to about 30%, 40% and 50%, respectively. It was found that the glass transition temperature (Tg) of about 21 ℃, 8 ℃ and -2 ℃ as the glass transition temperature (Tg) is the inverse of the plasticizer content. Example 3-2 (film with o-DBF) and Example 4-2 (film with o-DIAF) were likewise about 30%, 40% and 50% at 31 ° C, 21 ° C and 12 with increasing plasticizer content. Decreased to ° C. Therefore, when the glass transition temperature (Tg) is a thermal characteristic closely related to the flexibility of the material, it is understood that the more plasticizer is added, the lower the glass transition temperature (Tg) and the more flexible the material can be. Could.

Test Example 7 Comparison of Tensile Properties

FIG. 7A is a graph showing a change in elastic modulus (E-Modulus) according to the type of plasticizer, FIG. 7B is a graph showing a change in stress at break according to the type of plasticizer, and FIG. 7C is a breakage time according to the type of plasticizer. It is a graph showing the change in elongation at break. Tensile properties were measured using the Universal Testing Machine (UTM) of the Z005 model (Zwick Roell, Germany) based on the ASTM D882-12 standard and the results are shown in Table 10 below.

Sample n * Elongation
at break (%) Stress at break (MPa) E-Modulus
(MPa) Comparative Example 2 (30%) 7 166.95 ± 3.95 19.38 ± 0.92 314.2 ± 6.65 Comparative Example 2 (40%) 13 166.71 ± 5.16 14.78 ± 0.48 71.7 ± 6.4 Comparative Example 2 (50%) 7 169.93 ± 7.54 11.37 ± 0.48 28.5 ± 1.5 Example 3-1 (30%) 7 174.46 ± 7.87 13.91 ± 1.01 270.7 ± 7.7 Example 3-1 (40%) 10 130.22 ± 5.61 11.03 ± 0.48 68.3 ± 6.5 Example 3-1 (50%) 7 130.05 ± 3.60 8.46 ± 0.20 36.4 ± 1.4 Example 4-1 (30%) 7 185.57 ± 8.69 16.83 ± 0.97 222.5 ± 20.4 Example 4-1 (40%) 9 145.16 ± 3.85 12.80 ± 0.33 93.6 ± 7.8 Example 4-1 (50%) 7 143.86 ± 4.19 9.06 ± 0.29 27.6 ± 1.4 Example 3-2 (30%) 7 190.08 ± 5.37 14.68 ± 0.60 158.7 ± 22.2 Example 3-2 (40%) 9 169.76 ± 3.43 11.34 ± 0.41 77.1 ± 3.4 Example 3-2 (50%) 9 171.13 ± 4.85 9.58 ± 0.87 42.4 ± 2.0 Example 4-2 (30%) 7 170.97 ± 10.19 18.22 ± 0.69 164.4 ± 18.8 Example 4-2 (40%) 9 168.00 ± 6.55 12.60 ± 0.51 78.3 ± 7.4 Example 4-2 (50%) 8 184.71 ± 5.75 11.62 ± 0.32 57.8 ± 3.2

n is the number of test specimens.

According to Figures 7a and 10, the modulus of elasticity of Examples 3-1, 3-2, 4-1 and 4-2 at 40% and 50% in relation to the energy absorbed before fracture was It can be seen that the elastic modulus is larger or similar.

However, according to FIG. 7B and Table 10, the stress at break was smaller in Examples 3-1, 3-2, 4-1, and 4-2 than in Comparative Example 2.

In addition, the elongation at break of FIGS. 7C and 10 shows the highest elongation when Examples 3-1, 3-2, and 4-1 contain 30% of the plasticizer, but the amount of the plasticizer is 40-. It can be seen that the elongation does not increase even if the increase to 50%.

Thus, for Examples 3-1, 3-2, 4-1 and 4-2 comprising the plasticizers of Examples 1-1, 1-2, 2-1 and 2-2, the most commonly used comparison It can be seen that the properties similar to or better than Comparative Example 2 including the plasticizer of Example 1, based on this, the plasticizers of Examples 1-1, 1-2, 2-1 and 2-2 are most commonly It is believed that the plasticizer of Comparative Example 1, which is used but toxic, can be substituted.

Test Example 8: Thermal Gravimetric Analysis (TGA)

8 is a thermogravimetric analysis (TGA) curve of Examples 3-1, 3-2, 4-1 and 4-2, which was performed using a TGA 4000 System (PerkinElmer, USA). In addition, the analysis results are shown in Table 11 below.

Film T _5% (℃) T _10% (℃) T _25% (℃) T _50% (℃) T _75% (℃) % Residue _{650 ° C} Example 3-1 (50%) 223.68 249.05 272.40 297.23 402.60 7.866 Example 4-1 (50%) 237.15 255.91 278.79 301.33 404.77 8.970 Example 3-2 (50%) 237.92 256.93 281.25 297.93 399.06 7.033 Example 4-2 (50%) 211.74 254.17 286.31 307.21 386.85 6.868

According to Figure 8 and Table 11, the TGA curves of the films prepared according to Examples 3-1, 3-2, 4-1 and 4-2 appear to have a similar shape and have excellent thermal stability. Decomposition appeared in three stages. The first step was mainly due to the release and evaporation of the plasticizer at about 205 ° C and the next step at 385 ° C, which is related to the dehydrogenation reaction of PVC to form macromolecules with conjugated bonds. have. The final step, seen at 520 ° C, appears to be the newly formed macromolecules with cracking and pyrolysis.

Test Example 9: Migration Resistance

Migration of plasticizer refers to the phenomenon that some of the plasticizer mixed with the polymer resin flows out of the polymer resin, and when the spilled plasticizer enters the body, it inhibits the normal activity of the endocrine system that is directly involved in life activities or causes abnormal reactions. Because it triggers fatal harm, the migration of plasticizers should be suppressed as much as possible. In order to measure this, two experiments (extractability, ASTM D5227-13) and volatility (ASTM D1203-10) were conducted.

Test Example 9-1: Measurement of Volatile Loss

9 is a graph comparing the volatility of the plasticizer according to Examples 1-1, 1-2, 2-1 and 2-2 and Comparative Example 1, the results are shown in Table 12 below.

Hexane-extractable content Volatile content Comparative Example 1 (DOP) n = 5 14.14 ± 0.92 n = 3 3.27 ± 0.49 Example 1-1 (2,5-DBF) n = 5 13.54 ± 0.64 n = 3 16.19 ± 0.27 Example 2-1 (2,5-DIAF) n = 3 13.10 ± 0.46 n = 3 6.89 ± 0.40 Example 1-2 (2,3-DBF) n = 5 5.39 ± 0.39 n = 3 10.05 ± 0.83 Example 2-2 (2,3-DIAF) n = 3 7.89 ± 0.65 n = 3 8.24 ± 0.89

According to FIG. 9 and Table 12, the plasticizers of Examples 1-1, 1-2, 2-1, and 2-2 were found to have a lower volatile loss than the plasticizer of Comparative Example 1. In addition, the alkyl moieties of Examples 1-1, 1-2, 2-1, and 2-2 provided less steric performance than the ethylhexyl moiety of Comparative Example 1 to help entangle the PVC matrix. It is judged to give. Therefore, the plasticizers of Examples 1-1, 1-2, 2-1, and 2-2 all exhibited superior properties to those of Comparative Example 1.

Test Example 9-2: Determination of Hexane Extractability

10 is a graph comparing the amounts of the plasticizers according to Examples 1-1, 1-2, 2-1 and 2-2 and Comparative Example 1, which were discharged in hot hexane for 2 hours.

According to FIG. 10, in the plasticizers of Examples 1-1, 1-2, 2-1, and 2-2, there is an extra oxygen (O) atom in the aromatic furan ring, and the polarity thereof is greatly increased, thereby providing the plasticizer of Comparative Example 1. It can be seen that less extract than.

Therefore, the plasticizers of Examples 1-1, 1-2, 2-1, and 2-2 all exhibited superior properties to those of Comparative Example 1.

Test Example 10: The yield difference of the plasticizer according to the amount of the separating agent

Di-n-butyl Furancarboxylates were prepared in the same manner as in Examples 1-1 and 1-2, and the yields were compared. The results are shown in Table 13 below.

Separation amount of alcohol to alcohol (mol / mol) Di-n-butyl Furancarboxylates Yield (%) p-xylene / [p-xylene + 1-butanol] o-DBF + p-DBF 8.0 51 8.8 79 9.5 95 10.2 71 10.9 54

According to Table 13, it was found that the yield can be maximized by controlling the amount of the separating agent used.

The scope of the present invention is shown by the following claims rather than the above description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention. do.

Claims (16)

Preparing a compound represented by formula 1 and / or a compound represented by formula 2 by reacting galactaric acid with alcohol while removing water in the presence of an acid catalyst and a material separation agent, as shown in Scheme 1. Method for producing a furanedialkyl carboxylate comprising:
Scheme 1

In Scheme 1, R is C1-C10 straight chain alkyl group or C3-C10 ground alkyl group. The method of claim 1,
The method for producing the furanedialkyl carboxylate
(a) adding a galactaric acid, an alcohol, an acid catalyst, and a separating agent to prepare a mixed solution; And
(b) reacting the mixed solution with the galactaric acid and the alcohol while removing water to prepare a compound represented by Formula 1 and / or a compound represented by Formula 2; The production method of furan dialkyl carboxylate. The method of claim 2,
The step (b) is a method for producing a furan dialkylcarboxylate, characterized in that carried out at a temperature of 70 to 200 ℃. The method of claim 3,
Method (b) is a method for producing a furan dialkylcarboxylate, characterized in that carried out at a temperature of 100 to 170 ℃ of the mixed solution. The method of claim 2,
Method of producing a furan dialkylcarboxylate, characterized in that the esterification reaction is carried out in step (b). The method of claim 1,
The galactaric acid is obtained from galactose (galactose) characterized in that the production method of furan dialkyl carboxylate. The method of claim 1,
Alcohol having a linear or pulverized alkyl group consisting of 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, isopentanol, isobutanol and the like Method for producing a furan dialkylcarboxylate, characterized in that it comprises one or more selected from. The method of claim 1,
The catalyst comprises at least one selected from inorganic acids consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like, and organic acids containing functional groups such as sulfonic acid (-SO ₃ H) and carboxylic acid (-CO ₂ H). The production method of furan dialkyl carboxylate. The method of claim 8,
Method for producing a furan dialkylcarboxylate, characterized in that the catalyst is sulfuric acid. The method of claim 1,
The separating agent is selected from an aromatic hydrocarbon compound consisting of benzene, toluene, o-xylene, m-xylene, p-xylene and the like and a C6-C16 aliphatic hydrocarbon compound consisting of hexane, heptane, octane, decane, dodecane and the like. A method for producing a furan dialkylcarboxylate comprising at least one kind. The method of claim 10,
Method for producing a furan dialkyl carboxylate, characterized in that the separating agent is p-xylene. The method of claim 1,
Method for producing a furan dialkyl carboxylate, characterized in that the compound represented by the formula 1 or 2 is any one selected from the following structural formulas 3 to 6.

The method of claim 1,
Method for producing a furan dialkyl carboxylate, characterized in that the compound represented by the formula 1 or 2 is a compound represented by the formula (6). Plasticizer comprising a compound represented by the formula 1 or 2 below; And
Thermoplastic polymers; To
Polymer composition comprising:
[Formula 1]

[Formula 2]

In the above formula 1 and 2,
Each R is independently a C1-C10 straight chain alkyl group or a C3-C10 ground chain alkyl group. The method of claim 14,
The polymer is made of polyvinyl chloride, polyethylene, polypropylene, polybinyl alcohol, polyalkyl methacrylate, polyvinylbutyral, and the like. Chain Polymers and Polylactic Acid, Polyhydroxybutyral, Polyester, Polycarbonate, Polyamide, Polyurea, Polyurethane Polymer composition, characterized in that it comprises one or more selected from condensation polymers consisting of. The method of claim 14,
Polymer composition, characterized in that the polymer comprises polyvinyl chloride.

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