KR102096828B1 - Dimenthyl ester-based derivatives, preparing method thereof and its use - Google Patents

Abstract

상기 식에서, n은 1 내지 30의 정수이다.The present invention is a dimentyl ester-based derivative represented by the following Chemical Formula 1, and since the dimentyl ester-based derivative of the present invention is added to plastic plastics and has an excellent effect of increasing thermoplasticity, it is an eco-friendly plasticizer that can replace phthalate-based plasticizers. It can be usefully used as.
[Formula 1]

In the above formula, n is an integer from 1 to 30.

Description

Dimenthyl ester-based derivatives, preparing method thereof and its use

The present invention relates to a dimentyl ester-based derivative, a method for manufacturing the same, and uses thereof, and an efficient method for manufacturing a dimentyl ester-based derivative using menthol as an environmentally friendly alcohol and a utilization method as a plasticizer to replace the phthalate-based plasticizer. present.

Menthol is a natural-based alcohol extracted from mint flavoring and flavoring mint, and is widely used in the food and pharmaceutical industries. It is typically used in toothpaste, oral hygiene products, fragrances, antibacterial agents, and preservatives, and it is contained in the peppermint oil we consume in a ratio of 30-50%. The substances ingested in this way support the evidence that they are non-toxic and safe.

On the other hand, a plasticizer is a plastic additive that refers to a material that makes polymer resins flexible and easy to process. That is, when added to PVC, it hardens and breaks the fragile glassy material, making it easy to mold. These plasticizers are considered to be good plasticizers with low volatility, stable heat and cold, flexibility at low temperatures, good mixing properties with rubber and plastic, and low elution. In addition, plasticizers are used to improve functions such as electrical insulation, adhesion, and cold resistance. Currently, it is mostly added to synthetic resins.

Plasticizers include di- (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diisononyl phthalate, DINP), phthalate plasticizers such as polyethylene terephthalate (PET), adipate plasticizers such as dioctyladipate (DOA), diisononyl adipate (DINA), fatty acid plasticizers, and phosphoric acid System plasticizers, polyester plasticizers, etc. have been used, of which phthalate plasticizers are the most used because of their excellent compatibility with PVC and high plasticizing efficiency, and the most widely used plasticizer is DEHP, which accounts for 72% of domestic plasticizer production. Occupy.

However, due to the problem that the phthalate-based plasticizer acts as an endocrine disruptor when exposed to the human body, use restrictions are being strengthened. Phthalate-based plasticizers have been designated as hazardous substances in developed countries such as Europe (EU) and domestic plastics have been classified as presumed environmental hormones, and since 2006, they have been banned for use in all plastic toys and children's products. In Korea, phthalate-based plasticizers were classified as presumed environmental hormones, and since 2006, their use has been banned for all plastic toys and children's products.

To replace these phthalate-based plasticizers, German company BASF developed Hexamoll ^® DINCH (1,2-cyclohexane dicarboxylic acid diisononyl ester), a structure that eliminates double bonds in the structure of phthalate-based plasticizers, but in the case of DINCH, reacted phthalate-based compounds It has the disadvantage that it can be detected.

Due to the harmfulness of the phthalate-based plasticizer, there is a need to develop a bio-based eco-friendly plasticizer having low elution and non-toxicity that can replace it.

The present inventors, while researching for the development of an eco-friendly plasticizer, produced a new dimentyl ester-based derivative, and confirmed that the dimentyl ester-based derivative is added to a plastic to increase the thermoplasticity and the effect is very excellent. Completed.

An object of the present invention is to provide a novel dimentyl ester-based derivative.

In addition, an object of the present invention is to provide a method for producing the dimentyl ester-based derivative.

Another object of the present invention is to provide a use as a plasticizer comprising the dimentyl ester-based derivative.

The present invention provides a dimentyl ester-based derivative represented by Formula 1:

[Formula 1]

In addition, the present invention provides a method for producing the dimentyl ester-based derivative.

In addition, the present invention provides a use as a plasticizer comprising the dimentyl ester-based derivative.

The dimentyl ester-based derivatives of the present invention are very good in adding thermoplasticity to increase thermoplasticity, and thus can be usefully used as an eco-friendly plasticizer that can replace phthalate-based plasticizers.

1 is a view schematically showing a method of manufacturing a PVC film.

The present invention provides a dimentyl ester-based derivative represented by Formula 1 below.

[Formula 1]

In the above formula, n is an integer from 1 to 30, preferably 4 to 12.

Preferably, the compound of Formula 1 may include at least one compound selected from the group consisting of the following Formulas 1-1 to 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In addition, the present invention (a) menthol, fatty acid, a solvent and a step of mixing and reacting the catalyst; comprising, providing a method for producing a dimentyl ester-based derivative represented by the following formula (1).

[Formula 1]

In the above formula, n is an integer from 1 to 30.

In step (a), the solvent may be at least one selected from the group consisting of aromatic solvents such as toluene, aliphatic organic solvents such as normal-hexane, cyclohexane, and mixtures thereof.

The organic solvent may be 50 to 1000 parts by weight based on 100 parts by weight of the mixture of menthol and fatty acids.

In step (a), the reaction may be preferably performed at 25 to 200 ° C, and more preferably 50 to 150 ° C.

In step (a), the reaction may be performed for 1 to 40 hours, and more preferably, for 20 to 40 hours.

In step (a), the fatty acid may be represented by the following Chemical Formula 2:

In the above formula, n is an integer from 1 to 30.

The fatty acid may be at least one selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, preferably composed of 4 to 12 carbon atoms.

In the step (a), p-toluene sulfonic acid, inorganic acid hydrochloric acid, sulfuric acid, etc. may be used as the Lewis acid catalysts such as aluminum, titanium, tin, zinc, etc., preferably titanium butoxide, p- It may be toluene sulfonic acid, titanium chloride, zinc chloride, hydrochloric acid, aluminum chloride, tin chloride, and more preferably titanium butoxide.

The catalyst may be used in an amount of 0.1 to 50 mol% based on fatty acids.

In step (a), the menthol and acid may be preferably mixed at a molar ratio of 1: 1 to 6: 1, and preferably at a molar ratio of 2: 1 to 4: 1.

In addition, the method

(b) adding sodium bicarbonate solution after the reaction, and extracting with ether; And

(c) drying and filtering after repeating the extraction; may further include.

The extraction in step (b) utilizes an acid-base reaction.

In step (c), MgSO ₄ may be used for drying, ether may be removed through vacuum rotary evaporation, and unreacted menthol may be removed through distillation under reduced pressure.

In addition, the present invention provides a use as a plasticizer comprising a dimentyl ester-based derivative represented by Formula 1 below.

[Formula 1]

In the above formula, n is an integer from 1 to 30.

The dimentyl ester-based derivative prepared in the present invention has excellent free compatibility, plasticity, thermal stability, and elution as a plasticizer because it has a large free volume due to the cyclo structure possessed by menthol, less chain entanglement, and high molecular mobility. Do.

Therefore, the dimentyl ester-based derivative of the present invention is added to plastic plastics and has an excellent effect of increasing thermoplasticity, and thus can be usefully used as an eco-friendly plasticizer that can replace phthalate-based plasticizers.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

Example  1. [Formula 1] of  Preparation of compounds

[Formula 1]

1-1. [Formula 1- 1] of  Preparation of compounds

[Formula 1-1]

The reaction was carried out at 110 ° C. for about 33 hours using 0.25 mol of menthol, 0.1 mol of adipic acid and toluene as a solvent, and using titanium butoxide 1 mol% / acid as a catalyst. After the reaction was completed, ether and saturated sodium bicarbonate solution were added, and separation extraction using an acid-base reaction was performed. After repeated extraction, the organic layer was washed with water and dried using MgSO ₄ .

Subsequently, it was filtered through a filtration process, ether was removed through a vacuum rotary evaporator, and unreacted menthol was removed through distillation under reduced pressure to finally obtain a compound represented by [Chemical Formula 1-1] with a yield of 78.1%. The structure of the synthesized compound was confirmed through 1H-NMR, and is shown in Table 2 below.

1-2. [Formula 1-2] to [Formula 1- 6]  Preparation of compounds

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In the same manner as in Example 1-1, [Chemical Formula 1-2] to [Chemical Formula 1-6] were prepared, and the types and capacities of mixed menthol and fatty acids, solvents and catalysts are shown in Table 1 below. The structures of the synthesized compounds were confirmed through 1H-NMR, respectively, and are shown in Table 2 below.

Alcohol fatty acid menstruum catalyst Reaction temperature time yield Kinds mol Kinds mol Kinds Kinds mol% ℃ hour % menthol 0.25 Adipic acid 0.1 toluene Titanium butoxide One 110 33 78.1 menthol 0.25 Adipic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 72.5 menthol 0.25 Adipic acid 0.1 toluene Titanium chloride One 110 34 70.5 menthol 0.3 Adipic acid 0.1 toluene Zinc chloride One 110 20 68.8 menthol 0.3 Adipic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 74.4 menthol 0.4 Adipic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 70.2 menthol 0.25 Pimelic acid 0.1 toluene Titanium butoxide One 110 33 90.7 menthol 0.25 Pimelic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 85.2 menthol 0.25 Pimelic acid 0.1 toluene Titanium chloride One 110 34 80.6 menthol 0.3 Pimelic acid 0.1 toluene Zinc chloride One 110 20 75.8 menthol 0.3 Pimelic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 80.2 menthol 0.4 Pimelic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 77.8 menthol 0.25 Suberic acid 0.1 toluene Titanium butoxide One 110 33 81.5 menthol 0.25 Suberic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 75.8 menthol 0.25 Suberic acid 0.1 toluene Titanium chloride One 110 34 80.0 menthol 0.3 Suberic acid 0.1 toluene Zinc chloride One 110 20 65.2 menthol 0.3 Suberic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 70.5 menthol 0.4 Suberic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 74.4 menthol 0.25 Azelaic acid 0.1 toluene Titanium butoxide One 110 33 88.7 menthol 0.25 Azelaic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 80.8 menthol 0.25 Azelaic acid 0.1 toluene Titanium chloride One 110 34 82.5 menthol 0.3 Azelaic acid 0.1 toluene Zinc chloride One 110 20 84.1 menthol 0.3 Azelaic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 70.5 menthol 0.4 Azelaic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 80.0 menthol 0.25 Sebacic acid 0.1 toluene Titanium butoxide One 110 33 69.6 menthol 0.25 Sebacic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 65.4 menthol 0.25 Sebacic acid 0.1 toluene Titanium chloride One 110 34 66.1 menthol 0.3 Sebacic acid 0.1 toluene Zinc chloride One 110 20 67.2 menthol 0.3 Sebacic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 66.1 menthol 0.4 Sebacic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 59.8 menthol 0.25 Dodecanedioic acid 0.1 toluene Titanium butoxide One 110 33 71.4 menthol 0.25 Dodecanedioic acid 0.1 Cyclohexane p-toluenesulfonic acid One 80 30 70.6 menthol 0.25 Dodecanedioic acid 0.1 toluene Titanium chloride One 110 34 64.7 menthol 0.3 Dodecanedioic acid 0.1 toluene Zinc chloride One 110 20 63.8 menthol 0.3 Dodecanedioic acid 0.1 Normal-hexane p-toluenesulfonic acid One 70 25 68.4 menthol 0.4 Dodecanedioic acid 0.1 Cyclohexane Hydrochloric acid 5 80 30 61.7

Chemical shift (ppm) Formula 1-1 4.54-4.68 (2H, m), 2.18-2.29 (4H, t), 1.85-1.98 (2H, m), 1.68-1.85 (2H, m), 0.88-1.67 (18H, m), 0.63-0.88 (18H , m) Formula 1-2 4.61-4.75 (2H, m), 2.21-2.34 (4H, t), 1.92-2.04 (2H, m), 1.78-1.92 (2H, m), 0.95-1.74 (20H, m), 0.71-0.95 (18H , m) Formula 1-3 4.54-4.67 (2H, m), 2.16-2.25 (4H, t), 1.83-1.98 (2H, m), 1.71-1.83 (2H, m), 0.88-1.67 (22H, m), 0.63-0.88 (18H , m) Formula 1-4 4.61-4.75 (2H, m), 2.21-2.34 (4H, t), 1.90-2.03 (2H, m), 1.79-1.90 (2H, m), 0.95-1.74 (24H, m), 0.69-0.95 (18H , m) Formula 1-5 4.53-4.67 (2H, m), 2.16-2.24 (4H, t), 1.83-1.96 (2H, m), 1.72-1.83 (2H, m), 0.88-1.67 (26H, m), 0.65-0.88 (18H , m) Formula 1-6 4.60-4.74 (2H, m), 2.23-2.31 (4H, t), 1.91-2.04 (2H, m), 1.77-1.91 (2H, m), 0.95-1.74 (30H, m), 0.71-0.95 (18H , m)

Example  2. Comparative example  Preparations

As a comparative example of the dimentyl ester-based compound of the present invention, the most commercially available phthalate plasticizer DEHP (represented by [Chemical Formula C-1]) and non-phthalate plasticizer DINCH (represented by [Chemical Formula C-2]) were prepared. .

[Chemical Formula C-1]

[Chemical Formula C-2]

Experimental example  1. Manufacturing of PVC film

PVC films were prepared for evaluation of compatibility, plasticity, thermal stability, and elution as a plasticizer for the compounds prepared according to the above Examples and Comparative Examples, and the production process is schematically illustrated in FIG. 1.

Experimental example  2. Evaluation of compatibility through solubility parameter

In order to evaluate the compatibility of the dimentyl ester-based compound of the present invention prepared through Example 1 with DEHP and DINCH prepared as Comparative Examples in Example 2 as plasticizers, the solubility parameter was calculated through Equation 1 below. The results are shown in Table 3 below.

The dissolution parameter can predict the compatibility of the plasticizer on the principle of "like dissolves like". Usually, the difference in dissolution parameters between plasticizer and PVC is less than 3.7 (J / cm ³ ) ^1/2 , so it is judged to have excellent compatibility. That is, the difference in dissolution parameters of PVC was calculated and compared with DEHP, a phthalate-based plasticizer, and DINCH, a non-phthalate-based plasticizer, to evaluate the compatibility of the compound of the present invention as a plasticizer.

[Equation 1]

^{δ (J / cm 3) 1} /2 difference δ PVC 19.7 DEHP 18.25 1.45 DINCH 17.36 2.34 Formula 1-3 17.66 2.04 Formula 1-4 18.29 1.41 Formula 1-5 17.95 1.75 Formula 1-6 17.75 1.95

As shown in Table 3, the compounds represented by [Chemical Formula 1-3], [Chemical Formula 1-5] and [Chemical Formula 1-6] have somewhat lower compatibility than the phthalate plasticizer DEHP, but are commercially available non-phthalate based It was confirmed that the compatibility was higher than that of the plasticizer DINCH.

In particular, in the case of the compound represented by [Chemical Formula 1-4], it was confirmed that not only the commercially available non-phthalate plasticizer DINCH was more compatible, but also more compatible than the phthalate plasticizer DEHP.

Therefore, it is judged that the compound according to the present invention is highly compatible.

Experimental example  3. Plasticization  Efficiency evaluation

In order to evaluate the plasticity of the dimentyl ester-based compounds of the present invention prepared through Example 1 and DEHP and DINCH prepared as Comparative Examples in Example 2, the glass transition temperature measured by differential scanning calorimetry (DSC) was Substituting in Equation 2, the glass transition temperature and plasticizing efficiency of the examples were measured. After comparing the glass transition temperature of PVC without plasticizer and the glass transition temperature of PVC with plasticizer, it was measured and compared with DEHP and DINCH, the plasticizing efficiency was evaluated, and the results are shown in Table 4 below. .

[Equation 2]

E _{△ Tg} (%)

Plasticizing efficiency (%) Tg (℃) DEHP Compared to DINCH NON 45.59 - - Formula C-1 -One - - Formula 1-1 -2.93 104.1 115.7 Formula 1-2 -3.99 106.4 118.2 Formula 1-3 -4.19 106.8 118.7 Formula 1-4 -4.01 106.5 118.2 Formula 1-5 -2.4 103.0 114.4 Formula 1-6 -3.64 105.7 117.4

As shown in Table 4, the plasticizer compounds represented by [Chemical Formula 1-1] to [Chemical Formula 1-6] have significantly lower plasticizing efficiency than phthalate DEHP, but have significantly better plasticizing efficiency than commercially available non-phthalate plasticizer DINCH. It was shown. This is presumed to be because the cyclo structure possessed by menthol has a large free volume, less chain entanglement and high molecular mobility.

Therefore, it was confirmed that the compounds of [Chemical Formula 1-1] to [Chemical Formula 1-6] according to the present invention can improve plasticizing efficiency.

Experimental example  4. Thermal stability  evaluation

In order to evaluate the plasticity of the dimentyl ester-based compounds of the present invention prepared through Example 1 and DEHP and DINCH prepared as Comparative Examples in Example 2, thermal stability was measured by thermogravimetric analysis (TGA) and measured. Decomposition temperatures of 5%, 10%, and 50% of the examples are shown in Table 5 below.

DEHP
(℃) Formula 1-1
(℃) Formula 1-2
(℃) Formula 1-3
(℃) Formula 1-4
(℃) Formula 1-5
(℃) Formula 1-6
(℃) 5% 212.1 197.8 215.2 225.4 233.9 239.7 250.1 10% 235.5 228.0 240.8 245.8 252.8 256.3 265.1 50% 292.0 296.2 296.7 299.2 300.4 302.3 307.4

As shown in Table 5, the compounds represented by [Chemical Formula 1-1] to [Chemical Formula 1-6] did not show a weight change at 180 ° C or lower. Since the processing temperature of PVC products is 180 ℃, there should be no change in the weight of plasticizer at this temperature, so it is suitable as a plasticizer for PVC products. In addition, it was confirmed that the compounds represented by [Chemical Formula 1-2] to [Chemical Formula 1-6] had better thermal stability than the phthalate plasticizer DEHP.

As a result of the measurement, the thermal stability tends to increase as the number of carbon atoms increases. This is presumed to be because, as the alkyl chain, which is the non-polar part of the compound, increases linearly, the bonding force between the PVC molecular chain and the non-polar part between the compounds increases due to the van der Waals force.

Experimental example  5. Dissolution properties  evaluation

In order to evaluate the plasticity of the dimentyl ester-based compounds of the present invention prepared through Example 1 and DEHP and DINCH prepared as Comparative Examples in Example 2, their dissolution properties were evaluated. After measuring the weight ( W ₁ , W ₂ ) before and after the test using a soft PVC film (10 × 10 mm), it was calculated through Equation 3 below, and the results are shown in Table 6 below.

[Equation 3]

DW OIL EtOH NON 0.01 0.01 0.02 DEHP 0.03 1.29 0.35 Formula 1-1 0.15 0.57 0.15 Formula 1-2 0.14 0.43 0.14 Formula 1-3 0.12 1.06 0.31 Formula 1-4 0.14 0.85 0.29 Formula 1-5 0.13 1.04 0.29 Formula 1-6 0.06 1.12 0.21

As shown in Table 6, it was confirmed that the dissolution properties of the compounds according to the present invention were excellent overall.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (13)

Plasticizer comprising a dimentyl ester-based derivative represented by the following formula (1):
[Formula 1]

In the above formula, n is an integer from 1 to 30.
The plasticizer according to claim 1, wherein n is 4 to 12.
According to claim 2, wherein the compound of Formula 1 is characterized in that represented by the following Formula 1-1 to 1-6, plasticizer:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

(A) mixing and reacting menthol, fatty acids, solvents and catalysts; comprising the method of manufacturing the plasticizer according to claim 1.
The method of claim 4, wherein the method
(b) adding sodium bicarbonate solution after the reaction, and extracting with ether; And
(c) drying and filtering after repeating the extraction; further comprising a method of manufacturing a plasticizer.
The method of claim 4, wherein the reaction of step (a) is performed at 50 to 150 ° C.
The method of claim 4, wherein the fatty acid in step (a) is represented by the following Chemical Formula 2.
[Formula 2]

In the above formula, n is an integer from 1 to 30.
The method of claim 7, wherein the fatty acid is at least one selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
The method of claim 4, wherein the menthol and fatty acids in step (a) are mixed in a molar ratio of 2: 1 to 4: 1.
[6] The catalyst according to claim 4, wherein the catalyst in step (a) is at least one selected from the group consisting of titanium butoxide, p-toluenesulfonic acid, titanium chloride, zinc chloride, hydrochloric acid, aluminum chloride and tin chloride. , Plasticizer manufacturing method.
The method according to claim 4, wherein the solvent of step (a) is at least one selected from the group consisting of toluene, normal-hexane and cyclohexane. delete delete

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