KR102471310B1 - A citrate- based plasticizer composition and a resin composition comprising the same - Google Patents

Abstract

The present invention relates to a citrate-based plasticizer composition and a resin composition comprising the same, wherein the citrate-based plasticizer composition is produced by a reaction of citric acid and one or more alcohols selected from 2-ethylhexanol, 2-octanol or n-octanol, and thus the composition is not harmful to the human body and can solve the problems of volatility and aging resistance of existing phthalate-based plasticizer compositions.

Description

A citrate-based plasticizer composition and a resin composition comprising the same

The present invention relates to a citrate-based plasticizer composition and a resin composition comprising the same.

In general polymers, mutual forces between molecules act. The mutual force between the polymer molecules is generated by the force between the polar and non-polar molecules of the polymer chain. The stronger this force, the smaller the fluidity between the polymer molecules constituting the resin. Therefore, the stronger the inter-molecular force of the polymer, the harder it is and the more difficult it is to process. Polymeric resins should be given flexibility and processability for use in applications such as sheets, artificial leather, wallpaper, paints, sealants, and foam mats. At this time, a plasticizer is added to the polymer resin composition.

The plasticizer penetrates between the polymer chains and serves to relieve the forces between the molecules. In general, plasticizers are adipate-based and phthalate-based plasticizers produced by an ester reaction between a carboxylic acid such as adipic acid or phthalic acid and an alcohol. Examples of commercially available primary plasticizers include di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, and di(ethylhexyl)phthalate, diisononyl phthalate, and diisodecyl phthalate. can

However, through many studies, commercialized phthalate-based plasticizers have been found to disrupt the endocrine system with endocrine disruptors. In the case of adipate-based plasticizers, regulations are weak compared to phthalate-based plasticizers, but in the case of (2-ethylhexyl) adipate, the amount of use is regulated with respect to cooking utensils, food containers, and food packaging.

The phthalate-based plasticizer was regulated for infants and teenagers such as baby products and children's toys by the National Environment Agency in 2010 in Korea. And in 2012, it was applied to wallpaper and flooring, and it was expanded to the limit of commercial use. Due to the regulation, the amount of the phthalate-based usage is limited, and the physical properties of the resin composition to which a sufficient plasticizer is added before the regulation cannot be implemented.

Therefore, we are focusing on developing new plasticizers that can replace adipate-based plasticizers or phthalate-based plasticizers. A representative plasticizer that can replace the adipate-based plasticizer or the phthalate-based plasticizer is a citrate-based plasticizer. Conventional citrate-based plasticizers were synthesized by esterification of citric acid and alcohols having 2 to 4 carbon atoms, and were used as secondary plasticizers. However, due to problems such as low heat resistance or heating loss of these products, it is difficult to apply as a single plasticizer or primary plasticizer used in high content.

Therefore, many researches are needed to use the citrate-based plasticizer as the primary plasticizer. In addition, in terms of various physical properties such as non-environmental hormones and resin processability, volatility, tensile strength, migration loss, thermal loss, etc. through the citrate-based plasticizer composition, development of a plasticizer composition that sufficiently improves the adipate-based or phthalate-based plasticizer need this

Korean Patent Publication No. 2017-0064749

In order to solve the problems of the prior art as described above, the present invention is prepared by reacting one or two or more alcohols selected from 2-ethylhexanol, 2-octanol or n-octanol with citric acid, harmless to the human body and It is an object of the present invention to provide a citrate-based plasticizer composition having excellent environmental friendliness.

In order to solve the above problems, the present invention provides a citrate-based plasticizer composition prepared by esterification of citric acid with one or two or more alcohols selected from 2-ethylhexanol, 2-octanol and n-octanol. .

In one embodiment of the present invention, the citrate-based plasticizer composition is prepared by an esterification reaction of citric acid and one alcohol selected from 2-ethylhexanol, 2-octanol and n-octanol. can

In another embodiment of the present invention, a citrate-based plasticizer composition prepared by an esterification reaction of citric acid and a mixed alcohol of 2-ethylhexanol and 2-octanol may be provided.

In another embodiment of the present invention, a citrate-based plasticizer composition prepared by an esterification reaction of a mixed alcohol of citric acid, 2-ethylhexanol, and n-octanol may be provided.

In another embodiment of the present invention, a citrate-based plasticizer composition prepared by esterification of citric acid and a mixed alcohol of n-octanol and 2-octanol may be provided.

In another embodiment of the present invention, a citrate-based plasticizer composition prepared by an esterification reaction of citric acid and a mixed alcohol of 2-ethylhexanol, 2-octanol, and n-octanol can be provided. have.

The present invention may provide a resin composition including the above-described citrate-based plasticizer composition and a polymer resin.

In one embodiment of the present invention, the polymer resin is polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber or It may be selected from the group consisting of acrylic resins.

In one embodiment of the present invention, the resin composition may provide a resin composition containing 5 to 150 parts by weight of the citrate-based plasticizer composition based on 100 parts by weight of the polymer resin.

In another embodiment of the present invention, the resin composition contains any one or two or more selected from the group consisting of a secondary plasticizer, a filler, a lubricant, a stabilizer, a foaming agent, a viscosity modifier, a processing aid, a flame retardant, an enhancer, a pigment, and a dispersant. More may be included.

The present invention provides a molded article manufactured from the resin composition described above.

In the present invention, a plasticizer composition prepared by esterifying any one or two or more alcohols selected from 2-ethylhexanol, 2-octanol and n-octanol with citric acid is environmentally friendly and harmless to the human body, and thus replaces existing phthalate-based plasticizers. can be replaced

In addition, the resin composition including the citrate-based plasticizer composition and molded articles prepared therefrom can impart high elongation retention and volatility resistance, and the resin composition and molded articles can impart excellent aging resistance.

The citrate-based plasticizer composition of the present invention, a resin composition including the same, and a molded article made of the resin composition will be described in more detail through the following examples. However, the following examples are only references for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is merely to effectively describe specific embodiments and is not intended to limit the present invention.

In the present invention, the term concept of the citrate-based plasticizer composition may be a mixture of citrate-based plasticizers having different alkyl groups, rather than a single citrate-based plasticizer.

The present invention can provide a citrate-based plasticizer composition by esterifying any one or two or more alcohols selected from 2-ethylhexanol, n-octanol, and 2-octanol with citric acid.

It was found that a molded article made of a resin composition including the citrate-based plasticizer composition had excellent resistance to volatility, residual elongation, elongation, and tensile strength, thereby completing the present invention.

As a specific example, citric acid is a compound containing three carboxyl groups. Therefore, in the present invention, when a mixed alcohol of two or more alcohols selected from 2-ethylhexanol, n-octanol, and 2-octanol is reacted with citric acid, the alkyl group substituted for the carboxylic acid of citric acid is different from each other in citrates. based plasticizers can be prepared.

In one embodiment of the present invention, a citrate-based plasticizer composition prepared by esterifying citric acid with any one alcohol selected from 2-ethylhexanol, 2-octanol, and n-octanol may be provided.

In another embodiment of the present invention, the citrate-based plasticizer composition may be prepared by esterifying a mixed alcohol of 2-ethylhexanol and 2-octanol with citric acid.

In another embodiment of the present invention, the citrate-based plasticizer composition may provide a citrate-based plasticizer composition prepared by esterifying a mixed alcohol of 2-ethylhexanol and n-octanol with citric acid.

In another embodiment of the present invention, the citrate-based plasticizer composition may be prepared by esterifying n-octanol and 2-octanol mixed alcohol with citric acid.

In another embodiment of the present invention, the citrate-based plasticizer composition is prepared by esterifying a mixed alcohol of 2-ethylhexanol, 2-octanol and n-octanol with citric acid to provide a citrate-based plasticizer composition can

Specifically, the citrate-based plasticizer composition may be prepared by an esterification reaction of n-octanol with citric acid or an esterification reaction of a mixed alcohol containing n-octanol. The resin composition including the citrate-based plasticizer composition having one or more n-octyl groups and molded articles prepared therefrom may have excellent effects in terms of elongation residual rate and 100% modulus as well as volatilization loss.

Although described as a structural formula to aid understanding of the citrate-based plasticizer composition, the scope of the present invention is not limited to the structural formula.

The citrate-based plasticizer composition prepared in one embodiment of the present invention may include one or two or more selected from citrate represented by the following structural formula and isomers thereof.

The present invention may provide a resin composition including the citrate-based plasticizer composition and a polymer resin.

The polymer resin is a group consisting of polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, ethylene polymer, propylene polymer, polyketone, polystyrene, polyurethane, natural rubber, synthetic rubber or acrylic resin can be selected from.

Specifically, the polymer resin may be a resin having strong stress between polymer chains, such as a polyvinyl chloride resin, a polyolefin resin, or a polyester resin, and more specifically, it may be a polyvinyl chloride resin or a polyester resin, but is not limited thereto. .

According to one aspect of the present invention, the resin composition may include 5 to 150 parts by weight, preferably 20 to 100 parts by weight of the citrate-based plasticizer composition based on 100 parts by weight of the polymer resin, but achieve the object of the present invention It is not limited to this line.

In another embodiment of the present invention, the resin composition is any one or two or more selected from the group consisting of a secondary plasticizer, a filler, a lubricant, a stabilizer, a foaming agent, a viscosity modifier, a processing aid, a flame retardant, an enhancer, a pigment, and a dispersant may be further included.

Specifically, the filler may be a ceramic or metal-based material, for example, silica calcium carbonate, magnesium carbonate, calcium carbonate, talc, or the like. However, the filler does not limit its use in the art, especially for polyvinyl chloride resin compositions.

Specifically, the filler may include 1 to 200 parts by weight, more specifically 1 to 150 parts by weight, based on 100 parts by weight of the polymer resin, but is not limited thereto.

In addition, specifically, additives such as the stabilizer, UV stabilizer, flame retardant or lubricant may be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polymer resin, but is not limited thereto.

In the present invention, a molded article manufactured from a resin composition including the citrate-based plasticizer composition of one embodiment of the present invention may be provided.

The molded article has excellent elongation rate, elongation residual rate, volatility resistance, bleeding resistance and volatility resistance, so that the resin composition can provide excellent processability and excellent aging resistance.

Therefore, the molded article can be appropriately used in artificial leather, wires, films, sheets, and the like for automobiles.

Hereinafter, the present invention will be described in detail with reference to examples. However, these are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.

Example

<test items>

1. Measurement of tensile strength and elongation

It was measured according to the KS M 3156 standard. After pulling the crosshead speed to 200 mm / min, the cutting point of the specimen was measured. Tensile strength and elongation are calculated from the following formula.

Tensile strength (kgf/mm ² ) = load value (kgf)/thickness (mm)*width (mm) of the specimen

Elongation (%) = [length after extension/initial length] × 100

2. Renal residual rate

After the specimen was left in the aging condition of 121 ° C × 168 hours in a heating type aging tester (Geer Oven), the elongation was measured. Elongation was measured according to the KS M 3156 standard as described above. The elongation rate before and after the aging test was measured, and the elongation residual rate was calculated according to the following formula.

Residual elongation (%) = [elongation of specimen after aging / elongation of specimen before aging] × 100

The closer the calculated value is to 100%, the more similar mechanical properties are to those before aging, which means that durability/aging resistance, which is the maintenance of initial physical properties, is excellent.

3. Volatilization reduction

After leaving the specimen under aging conditions of 121 ° C × 168 hours in a heating type aging tester (Geer Oven), weight loss after heating (aging) was calculated according to the following formula. The smaller the weight loss after heating (aging), the better the aging resistance.

Volatilization loss (wt%) = (weight before aging - weight after aging) / weight before aging × 100

4. 100% modulus

It was measured according to the KS M 3156 standard. After pulling the crosshead speed at 200 mm/min, the tensile strength was measured at the point where the initial gauge line distance of the specimen is 2, that is, when the specimen is stretched 100% by tension. This means plasticization efficiency, and it is determined that the plasticization efficiency of the material is excellent as the 100% modulus value is lower.

Example 1: Preparation of citrate-based plasticizer composition (TEHC, tri 2-ethylhexyl citrate)

1 mol of citric acid and 3 mol of 2-ethylhexanol were added to the reactor, and 0.006 mol of PTSA (para-toluenesulfonic acid) as a catalyst was additionally added to the reactor. Then, a direct esterification reaction was performed by increasing the temperature to about 160 °C. During the direct esterification reaction, 0.9 mol of 2-ethylhexanol was additionally introduced into the reactor. After completion of the reaction, the reactant was purified. And the obtained compound was analyzed by GC-Mass.

Production of measurement samples

Based on 100 parts by weight of polyvinyl chloride resin (polymerization degree 1,000/Hanwha Solution P-1000 Grade), 70 parts by weight of the plasticizer composition of Example 1 and 2.5 parts by weight of a stabilizer (CZ-400 (Ca-Zn Organics, Songwon Industry) were added, . After that, the physical properties were measured and listed in Table 1 below.

Example 2: Preparation of citrate-based plasticizer composition (TNOC, tri n-octyl citrate)

The reaction was carried out in the same manner as in Example 1, except that n-octanol was used instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Example 3: Preparation of citrate-based plasticizer composition (T2OC, tri 2-octyl citrate)

The reaction was carried out in the same manner as in Example 1, except that 2-octanol was used instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Example 4: Preparation of citrate-based plasticizer composition (citrate mixture of 2-ethylhexyl and n-octyl)

The reaction was carried out in the same manner as in Example 1 except that 2-ethylhexanol and n-octanol were used in a molar ratio of 5:5 instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Example 5: Preparation of citrate-based plasticizer composition (citrate mixture of 2-ethylhexyl and 2-octyl)

The reaction was carried out in the same manner as in Example 1, except that 2-ethylhexanol and 2-octanol were used in a molar ratio of 5:5 instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Example 6: Preparation of citrate-based plasticizer composition (citrate mixture of n-octyl and 2-octyl)

The reaction was carried out in the same manner as in Example 1 except that n-octanol and 2-octanol were used in a molar ratio of 5:5 instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Example 7: Preparation of a citrate-based plasticizer composition (citrate mixture of 2-ethylhexyl, n-octyl and 2-octyl)

The reaction was performed in the same manner as in Example 1 except that 2-ethylhexanol, n-octanol, and 2-octanol were used in a molar ratio of 4:3:3 instead of 2-ethylhexanol in Example 1. was performed. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Comparative Example 1: Preparation of citrate-based plasticizer composition (THpC, tri(n-heptyl) citrate)

The reaction was carried out in the same manner as in Example 1, except that n-heptanol was used instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Comparative Example 2: Preparation of citrate-based plasticizer composition (THxC, tri (n-hexyl) citrate)

The reaction was carried out in the same manner as in Example 1, except that n-hexanol was used instead of 2-ethylhexanol in Example 1. Thereafter, a measurement sample was prepared in the same manner as in Example 1, and the physical properties thereof were measured and listed in Table 1 below.

Comparative Example 3: DIDP (di isodecyl phthalate)

Instead of the citrate-based plasticizer composition in the preparation of the measurement samples of Examples 1 to 7

Except for using DIDP (di isodecyl phthalate / Exxon Co.), measurement samples were prepared in the same way, and their physical properties were measured and listed in Table 1 below.

The tensile strength
(kgf/mm ² ) elongation rate
(%) renal residual rate
(%) 100% modulus (kgf/mm ² ) volatilization loss
(wt%) Example 1 1.4 354 75 0.68 8.9 Example 2 1.3 358 90 0.64 3.0 Example 3 1.4 355 66 0.70 10.1 Example 4 1.4 356 85 0.66 4.9 Example 5 1.4 355 79 0.69 9.3 Example 6 1.4 356 77 0.66 6.7 Example 7 1.4 357 80 0.65 5.3 Comparative Example 1 1.3 326 43 0.62 16.1 Comparative Example 2 1.2 324 35 0.60 21.3 Comparative Example 3 1.5 351 55 0.73 15.5

Examples 1 to 7 of the present invention are citrate-based plasticizer compositions prepared from alkyl alcohol having 8 carbon atoms in an alkyl group, Comparative Example 1 is a citrate-based plasticizer composition having 7 carbon atoms in an alkyl group, and Comparative Example 2 is a citrate-based plasticizer composition having an alkyl group having 8 carbon atoms It is a citrate-based plasticizer composition having 6 carbon atoms. Comparative Example 3 is a phthalate-based plasticizer, DIDP.

In Table 1, Examples 1 to 7 are equivalent to Comparative Example 3 in tensile strength and elongation. However, it can be confirmed that the elongation residual rate, 100% modulus and volatilization loss are better than those of Comparative Example 3. As a result, it was confirmed that DIDP, which is a conventional phthalate-based plasticizer, can be substituted and that aging resistance is more excellent.

In addition, looking at Examples 1 to 7 and Comparative Examples 1 to 2, it can be confirmed that the plasticizer composition of the present invention has excellent elongation rate, residual elongation rate and volatilization loss. As confirmed in the tensile strength and 100% modulus, it is confirmed that Comparative Examples 1 and 2 have better plasticization properties than the citrate plasticizer of the present invention. However, as described above, other physical properties are inferior to those of Examples 1 to 7, so it can be confirmed that it cannot be used in the field of replacing the DIDP plasticizer.

In the case of residual elongation and loss of volatilization, Examples 1 to 7 are superior to Comparative Example 1 and Comparative Example 2 in terms of physical properties that affect the weather resistance of molded products.

In particular, the resin composition and the molded article including the citrate-based plasticizer composition containing at least one n-octyl group had a volatilization loss of 6.7 wt% or less, which was significantly superior to the samples of Comparative Examples 1 to 3. In particular, the measurement sample of Example 2 including the citrate-based plasticizer composition obtained by esterification of citric acid and n-octanol alone showed a loss of volatilization of 3 wt%. Therefore, volatilization loss is a physical property showing the aging resistance and weather resistance of the resin, and the resin composition including the citrate-based plasticizer composition having an n-octyl group of the present invention and the molded article produced therefrom can maintain the initial physical properties for a long period of time. It has good weather resistance.

Through this, it can be confirmed that the citrate-based composition having an alkyl group having 8 carbon atoms of the present invention has a higher elongation rate than the citrate-based plasticizer composition having an alkyl group having 7 or 6 carbon atoms, and the citrate-based plasticizer composition of the present invention It was confirmed that this DIDP plasticizer can be replaced. In addition, as a result of confirming the elongation retention and volatility resistance of the citrate-based plasticizer composition of the present invention, it was confirmed that the weather resistance was excellent compared to Comparative Examples 1 to 3.

In conclusion, the citrate-based plasticizer composition of the present invention is superior to the existing phthalate-based or citrate-based plasticizer compositions having 6 to 7 carbon atoms in the alkyl group, and has excellent elongation retention and volatility resistance, and as a result, It can be seen that the molded article made of the resin composition has excellent aging resistance. Therefore, molded articles made of the resin composition can replace phthalate plasticizers in artificial leather, sheets, wires, wallpaper, and structures, and can provide better aging resistance.

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

Claims (11)

A citrate-based plasticizer composition prepared by esterifying at least one mixed alcohol selected from 2-ethylhexanol and 2-octanol, n-octanol, and citric acid. delete delete According to claim 1,
A citrate-based plasticizer composition prepared by esterifying a mixed alcohol of 2-ethylhexanol and n-octanol with citric acid. According to claim 1,
A citrate-based plasticizer composition prepared by esterifying a mixed alcohol of n-octanol and 2-octanol with citric acid. According to claim 1,
A citrate-based plasticizer composition prepared by esterifying a mixed alcohol of 2-ethylhexanol, 2-octanol and n-octanol with citric acid. A resin composition comprising the citrate-based plasticizer composition of any one of claims 1 and 4 to 6 and a polymer resin. According to claim 7,
The polymer resin is polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, ethylene polymer, polypropylene resin, polyketone resin, polystyrene resin, polyurethane resin, natural rubber, synthetic rubber or acrylic Any one or two or more resin compositions selected from the group consisting of resins. According to claim 7,
The resin composition is a resin composition comprising 5 to 150 parts by weight of the citrate-based plasticizer composition based on 100 parts by weight of the polymer resin. According to claim 7,
The resin composition further comprises any one or two or more selected from the group consisting of a secondary plasticizer, a filler, a lubricant, a stabilizer, a foaming agent, a viscosity modifier, a processing aid, a flame retardant, an enhancer, a pigment, and a dispersant. A molded article manufactured from the resin composition of claim 7.