WO2018056666A1 - Composite plasticizer composition, method for preparing same, and polymer resin composition using same - Google Patents

Abstract

The present invention relates to a composite plasticizer composition comprising a terephthalate derivative mixture and a dialkyl phthalate-based compound, a method for preparing the same, and a polymer resin composition comprising the same. The present invention provides a polymer resin composition having excellent physical properties, such as tensile strength, elongation, 100% modulus, elongation retention, and volatilization loss, etc., by using a composite plasticizer composition according thereto.

Description

Composite plasticizer composition, preparation method thereof, and polymer resin composition using same

The present invention relates to a composite plasticizer composition, a preparation method thereof, and a polymer resin composition using the same.

Polymer resins are used in various fields such as household goods, home appliances, clothing, automobiles, construction materials, packaging materials, etc. To date, polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU), polyvinyl chloride (PVC), and the like are widely used.

In particular, PVC resin is hard, soft properties, and can be molded in a variety of ways and excellent price competitiveness has a universal utility has been applied to various applications from household goods to industrial materials. These PVC resins can not be used alone, and added to the plasticizer to implement a variety of physical properties.

Plasticizers serve to impart flexibility to the PVC resin and to improve processability and compatibility. However, as the industry develops, plasticizers are not only flexible, but also diverse according to the characteristics required for their application fields such as aging resistance, cold resistance, oil resistance, water resistance, transition resistance, and heat resistance.

In general, the larger the molecular weight, the better the aging resistance, but the compatibility with the vinyl chloride resin tends to be lowered. Therefore, plasticizers suitable for aging resistance and compatibility are selected and used according to application fields. In addition, the plasticizer that satisfies the environmental regulation is excellent in room temperature and aging properties, but there is a problem that the workability is lowered.

For example, diisodecyl phthalate (DIDP), which has been conventionally used as a plasticizer for polymer resins such as polyvinyl chloride resin, has a high environmental hazard and imports a whole amount, although it can give very good properties to polymer resins. There is a problem that depends on (Korea No. 10-2015-0042159).

Therefore, in addition to such environmental regulations, the development of new plasticizers that can meet the requirements, such as physical properties, amount of use of plasticizers in accordance with industrial development is urgently needed.

In order to solve the above problems, the present invention provides an environment-friendly plasticizer that is harmless to the human body, and provides a polymer resin composition having excellent physical properties such as tensile strength, elongation rate, 100% modulus, elongation residual rate, volatilization loss, etc. by mixing it with a polymer resin. It aims to do it.

The present invention for achieving the above object is 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 30 of the compound of Formula 4 A terephthalate derivative mixture comprising 1 wt% to 70 wt% of the compound of Formula 5, and 1 wt% to 80 wt% of the compound of Formula 6; And a phthalate compound represented by Chemical Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound is 5 to 95:95 to 5.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

Moreover, another one aspect of this invention relates to the polymeric resin composition containing the said composite plasticizer composition.

Moreover, another one aspect of this invention relates to the molded article containing the said polymeric resin composition.

In still another aspect of the present invention, a) a reaction solution comprising 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and terephthalic acid is reacted to synthesize a terephthalate derivative mixture. step; And b) mixing the synthesized terephthalate derivative mixture with a phthalate compound of formula (7).

[Formula 7]

The composite plasticizer composition according to the present invention is an environmentally friendly plasticizer that is harmless to the human body, and has excellent compatibility and can provide a polymer resin composition having improved physical properties such as processability, heating loss, heat resistance, aging resistance, and weather resistance when mixed with a polymer resin. have.

Hereinafter, a composite plasticizer composition according to the present invention, a preparation method thereof, and a polymer resin composition using the same will be described in detail.

Unless otherwise defined in the technical and scientific terms used in the present invention, those having ordinary skill in the art to which the present invention belongs have the meanings that are commonly understood, and the gist of the present invention is unnecessary in the following description. Descriptions of well-known functions and configurations that may be blurred are omitted.

The inventors of the present invention have high environmental hazards and high imports, although diisodecyl phthalate (DIDP), which has been conventionally used as a plasticizer for polymer resins such as polyvinyl chloride resin, can impart very excellent properties to polymer resins. As a result of continuous research efforts to improve the problems depending on the results, the mixed plasticizer composition mixed with different kinds of terephthalate derivatives and di (2-propylheptyl) phthalate is an environmentally friendly plasticizer that is harmless to the human body and is inferior to DIDP. It has been found that the present invention provides the physical properties without which the present invention has been completed.

That is, the present invention relates to a composite plasticizer composition comprising a terephthalate derivative mixture, and di (2-propylheptyl) phthalate, and by using the same, provides an environmentally friendly plasticizer that is harmless to the human body, and mixes it with a polymer resin to increase tensile strength and elongation. It provides a polymer resin composition having excellent physical properties, such as 100% modulus, elongation residual ratio, volatilization loss.

Specifically, the composite plasticizer composition according to an embodiment of the present invention is 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, Formula 4 Terephthalate derivative mixture comprising 1 to 30% by weight of the compound, 1 to 70% by weight of the compound of Formula 5, and 1 to 80% by weight of the compound of Formula 6; And a phthalate compound represented by Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound may be 5 to 95: 95 to 5.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The composite plasticizer composition in which terephthalate derivative mixtures of different types and di (2-propylheptyl) phthalate are mixed in a specific ratio is an environmentally friendly plasticizer that is harmless to humans, and has excellent compatibility and processability and heating when mixed with a polymer resin. A polymer resin composition having improved physical properties such as weight loss, heat resistance, aging resistance, and weather resistance can be provided. On the other hand, when the compound of Formula 1 to the compound of Formula 6 alone is used, physical properties such as heat resistance, aging resistance, etc. may be poor, and when out of the weight% range, tensile strength, elongation, 100% modulus, elongation residual rate Or physical properties such as volatilization loss may be lowered.

More preferably, the composite plasticizer composition according to an embodiment of the present invention is 1 to 10% by weight of the compound of Formula 1, 5 to 15% by weight of the compound of Formula 2, 10 to 40% by weight of the compound of Formula 3, Compound 5 of Formula 4 Terephthalate derivative mixture comprising 15 wt%, 10-30 wt% of compound of Formula 5, and 10-40 wt% of compound of Formula 6; And a phthalate compound represented by Chemical Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound may be 20 to 40:80 to 60.

By satisfying the above range, when mixed and used in the polymer resin, it is possible to give the polymer resin a similar or better mechanical and aging properties than the commercial plasticizer DIDP. Specifically, excellent tensile strength of 1.5 to 2.0 kfg / mm 2, elongation of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm 2, elongation of 78 to 90%, and volatilization loss of 0 to 7% by weight. It may have physical properties, and the bleeding phenomenon may not occur. In this case, each physical property may be measured according to a measuring method to be described later.

The method for producing a composite plasticizer composition includes a) synthesizing a terephthalate derivative mixture by reacting a reaction solution containing 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and terephthalic acid. step; And b) mixing the synthesized terephthalate derivative mixture with a phthalate compound represented by Formula 7 below.

[Formula 7]

Specifically, step a) according to an embodiment of the present invention, with respect to 1 mol (mol) of terephthalic acid, 0.2-0.5 mol of 2-ethyl-1-hexanol, 0.4-0.8 mol of isononyl alcohol, 2-propyl-1 -Heptyl alcohol may be reacted with 0.8 ~ 1.2 moles. By satisfying such a range, 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 30% by weight of the compound of Formula 4, 1 to 70% by weight of the compound of Formula 5, and 1 to 80% by weight of the compound of Formula 6 may be synthesized.

At this time, step a) may be carried out for 10 to 20 hours at 230 ~ 250 ℃. In such reaction conditions, the esterification reaction may be effectively performed, and the compound of Formula 1 to the compound of Formula 6 may be synthesized in the above ranges.

In one embodiment of the present invention, step b) is a step of mixing the synthesized terephthalate derivative mixture with a phthalate compound of formula (7), that is, di (2-propylheptyl) phthalate, the weight ratio of the terephthalate derivative mixture: phthalate compound is 5 to 95: may be 95 to 5. It is possible to provide a polymer resin composition having excellent compatibility in such a range, and improved physical properties such as workability, heating loss, heat resistance, aging resistance, and weather resistance when mixed with a polymer resin.

More preferably, the weight ratio of terephthalate derivative mixture: phthalate compound may be 20-40: 80-60. By satisfying the above range, tensile strength of 1.5 to 2.0 kfg / mm 2, elongation of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm 2, elongation of 78 to 90%, loss of volatilization of 0 to 7% by weight, etc. It may have excellent physical properties of, and the bleeding phenomenon may not occur.

In addition, as mentioned above, the composite plasticizer composition according to the present invention may be applied to a polymer resin. That is, the present invention can provide a polymer resin composition containing a composite plasticizer composition.

In one embodiment of the present invention, the polymer resin is not necessarily limited thereto, but may include polyvinyl chloride resin, olefin resin, ABS resin, acrylic resin, polyester resin, and the like, preferably polyvinyl chloride (PVC). ) May be a resin. As such, by applying the composite plasticizer composition according to the present invention to the polyvinyl chloride resin, it is possible to maximize the improvement of physical properties such as tensile strength, elongation rate, 100% modulus, elongation residual rate, and volatilization loss.

In one example of the present invention, the composite plasticizer composition may be added in an amount of 20 to 120 parts by weight, more preferably 30 to 100 parts by weight, and more preferably 40 to 90 parts by weight, based on 100 parts by weight of the polymer resin. . In such a range, physical properties such as tensile strength, elongation rate, 100% modulus, elongation residual rate, and volatilization loss can be improved. Particularly, when polyvinyl chloride resin is used as the polymer resin and satisfies the above range, 1.5 to 2.0 kfg / It has excellent physical properties such as tensile strength of 2 mm2, elongation rate of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm2, elongation residual ratio of 78 to 90%, and volatilization loss of 0 to 7% by weight. This may not occur.

In addition, the polymer resin composition may further include any one or two or more additives selected from secondary plasticizers, stabilizers, fillers, lubricants, flame retardants, viscosity regulators, foaming agents, enhancers and pigments. The additive is not particularly limited, but may be added in an amount of 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polymer resin. Each additive in the above range can achieve the desired effect.

In addition, the present invention can provide a molded article prepared from the polymer resin composition described above. Specifically, the molded article may be silver wallpaper, compound, wire compound, sheet, film, tarpaulin, hose, shoes, sealant, office supplies, gloves, caps, mats, gaskets, food packaging materials, medical supplies, automotive products, toys, baby products, Floor materials, electromechanical parts, etc. can be used in various ways.

Hereinafter, the composite plasticizer composition, the preparation method thereof, and the polymer resin composition including the same according to the present invention will be described in more detail with reference to Examples. However, the following examples are only one reference for describing the present invention in detail, and 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 meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to be limiting of the invention. In addition, the unit of the additive which is not specifically described in the specification may be wt%.

First, the physical properties of the prepared specimens were measured in the following manner.

1) Tensile strength (kfg / mm2): Conducted according to KS M 3156.

2) Elongation (%): It was performed according to KS M 3156.

3) 100% Modulus (kfg / mm2): Tensile strength when the test piece is 100% elongated by tension, which means plasticization efficiency. The lower the 100% modulus value, the better the plasticization efficiency of the material. do.

4) Elongation Residual Rate (%): After leaving the test piece in aging conditions at 113 ° C. and 168 hours in a Geer Oven, the test piece was calculated as (test piece elongation strength after aging / test piece elongation before aging) × 100. The closer this value is to 100%, the similar mechanical properties as before aging. This property means the durability to the extent that the wire compound can maintain and use the initial properties for how long. Elongation strength of the test piece was conducted according to KS M 3156.

5) Volatilization loss (% by weight): After leaving the test piece to aging conditions at 113 ° C. and 168 hours in a Geer Oven, it was calculated as (weight of test piece after aging / weight of test piece before aging) × 100.

[ Example  One]

158 g of 2-ethyl-1-hexanol, 263 g of isononyl alcohol, 481 g of 2-propyl-1-heptyl alcohol and 389 g of terephthalic acid were esterified at 240 ° C for 18 hours.

After the reaction was completed, purification was performed to obtain a mixture of terephthalate derivatives in which the compound of Formula 1 to the compound of Formula 6 were mixed.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

As a result of analyzing the obtained terephthalate derivative mixture by GC-Mass analyzer, the weight percentage of the formula 1: formula 2: formula 3: formula: formula 4: formula 5: formula 6 is 5: 10: It confirmed that it was 30: 10: 15: 30.

Next, 70 parts by weight of di (2-propylheptyl) phthalate (DPHP, Di (2-propylheptyl) phthalate) was mixed with respect to 30 parts by weight of the obtained terephthalate derivative mixture to prepare a composite plasticizer composition.

[ Example  2]

The weight percent of each compound in the mixture of terephthalate derivatives was varied by varying the amount of the alcohol compound added. The weight% of the compound of Formula 1: Formula 2: Formula 3: Formula 4: Formula 5: Formula 6 was 8: 12: 28: 10: 15: 27 All the procedures except for the same were carried out in the same manner as in Example 1.

[ Example  3]

The weight percent of each compound in the mixture of terephthalate derivatives was changed by varying the amount of the alcohol compound to be added as 12: 18: 35: 9: 21: 5 All the procedures except for the same were carried out in the same manner as in Example 1.

[ Example  4]

All processes other than preparing the composite plasticizer composition by mixing 75 parts by weight of di (2-propylheptyl) phthalate with respect to 25 parts by weight of the terephthalate derivative mixture were carried out in the same manner as in Example 1.

[ Example  5]

All processes other than preparing a composite plasticizer composition by mixing 85 parts by weight of di (2-propylheptyl) phthalate with respect to 15 parts by weight of the terephthalate derivative mixture were carried out in the same manner as in Example 1.

[ Comparative example  One]

The weight percent of each compound in the mixture of terephthalate derivatives was changed by varying the amount of the alcohol compound, and the weight% of the formula 1: Formula 2: Formula 3: Formula 4: Formula 5: Formula 6: All the procedures except for the same were carried out in the same manner as in Example 1.

 [ Comparative example  2]

All the processes except for using 2-ethyl-1-hexanol and isononyl alcohol as the alcohol compound were carried out in the same manner as in Example 1, and the formula 1: Formula 2: Formula 3: Formula 4: Formula 5: Formula 6 A terephthalate derivative mixture was prepared in which the% was 30: 40: 0: 30: 0: 0.

[ Comparative example  3]

All the processes except for using isononyl alcohol and 2-propyl-1-heptyl alcohol as the alcohol compound were carried out in the same manner as in Example 1, and the formula 1: Formula 2: Formula 3: Formula 4: Formula 5: Formula 6 A terephthalate derivative mixture was prepared in which the% was 0: 30: 40: 0: 0: 30.

[ Comparative example  4]

All processes were carried out in the same manner as in Example 1 except that 2-ethyl-1-hexanol and 2-propyl-1-heptyl alcohol were used as the alcohol compound, and Chemical Formula 1: Chemical Formula 2: Chemical Formula 3: Chemical Formula 4: Chemical Formula 5 A terephthalate derivative mixture was prepared in which the weight percent of Formula 6 was 30: 0: 40: 0: 30: 0.

[ Comparative example  5]

All processes other than preparing the composite plasticizer composition by mixing 95 parts by weight of di (2-propylheptyl) phthalate with 5 parts by weight of the terephthalate derivative mixture were carried out in the same manner as in Example 1.

[ Comparative example  6]

All processes other than preparing the composite plasticizer composition by mixing 20 parts by weight of di (2-propylheptyl) phthalate with respect to 80 parts by weight of the terephthalate derivative mixture were carried out in the same manner as in Example 1.

Terephthalate Derivatives Mixture DPHP (parts by weight) One 2 3 4 5 6 Parts by weight Example 1 5 10 30 10 15 30 30 70 Example 2 8 12 28 10 15 27 30 70 Example 3 12 18 35 9 21 5 30 70 Example 4 5 10 30 10 15 25 25 75 Example 5 5 10 30 10 15 25 15 85 Comparative Example 1 30 5 10 30 10 15 30 70 Comparative Example 2 30 40 0 30 0 0 30 70 Comparative Example 3 0 30 40 0 0 30 30 70 Comparative Example 4 30 0 40 0 30 0 30 70 Comparative Example 5 5 10 30 10 15 25 3 97 Comparative Example 6 5 10 30 10 15 25 97 3

[Production Examples 1 to 5, and Comparative Production Examples 1 to 6]

Based on 100 parts by weight of polyvinyl chloride resin (PVC (paste resin, polymerization degree 1,000)), 70 parts by weight of the composite plasticizer composition prepared in Examples 1 to 5 and Comparative Examples 1 to 6, and a stabilizer (CZ-400, Complex of Ca-Zn organics, Songwon Industries) 2.5 parts by weight were added, respectively, and kneaded at 165 ° C. for 5 minutes using a Two-Roll Mill. Thereafter, a pressure of 15 MPa was applied at 175 ° C. for 3 minutes using a heat press, and after cooling to 90 ° C. or less, a specimen was prepared. The physical properties of the specimens were measured and their values are shown in Table 2 below.

[Comparative Manufacturing Example 7]

All processes other than using diisodecyl phthalate (DIDP) as a plasticizer were carried out in the same manner as in Preparation Example 1, and specimens were prepared. The physical properties of the specimens were measured and the values are shown in Table 2 below.

Plasticizer Tensile strength (kfg / ㎡) Elongation (%) 100% Modulus (kfg / mm2) Elongation Retention (%) Volatilization loss (% by weight) Breeding Preparation Example 1 Example 1 1.5 364 0.65 82 6 X Preparation Example 2 Example 2 1.5 360 0.65 79 7 X Preparation Example 3 Example 3 1.4 352 0.65 79 7 X Preparation Example 4 Example 4 1.5 360 0.65 78 6 X Preparation Example 5 Example 5 1.4 358 0.64 76 9 X Comparative Production Example 1 Comparative Example 1 1.4 352 0.66 75 8 X Comparative Production Example 2 Comparative Example 2 1.4 354 0.66 72 9 X Comparative Production Example 3 Comparative Example 3 1.5 351 0.72 81 6 O Comparative Production Example 4 Comparative Example 4 1.5 352 0.70 77 8 X Comparative Production Example 5 Comparative Example 5 1.5 357 0.63 72 9 X Comparative Production Example 6 Comparative Example 6 1.6 348 0.73 86 4 O Comparative Production Example 7 DIDP 1.5 351 0.68 80 6 X

As shown in Table 2, Preparation Examples 1 to 5 using a terephthalate derivative mixture and DPHP according to the present invention mixed with a specific ratio as a plasticizer, showed similar or better physical properties when compared to the commercial plasticizer DIDP can confirm.

On the other hand, in the terephthalate derivative mixture, in Comparative Preparation Example 1 in which the weight% of each compound is outside the weight% range of the present invention, it can be confirmed that elongation, residual elongation, and volatility decrease.

In addition, unlike the present invention, in Comparative Preparation Examples 2 to 4 using only two types of alcohol compounds, it can be seen that the elongation rate, elongation residual rate and volatilization loss are reduced or a bleeding phenomenon occurs.

In addition, in Comparative Preparation Examples 5 and 6 in which the weight part of the DPHP is out of the range of the present invention, it can be confirmed that the elongation rate, the elongation remaining rate and the volatilization loss are reduced or the bleeding phenomenon occurs.

As such, it was confirmed that the effect of using the compound of the formula (1) to the compound of the formula (6) is excellent, and also, the mixing ratio of each terephthalate derivative compound, and the mixing ratio of DPHP affects the performance of the composite plasticizer. Could confirm.

Although the present invention has been described through the specific matters and the limited embodiments as described above, it is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention belongs to Those skilled in the art can make various modifications and variations from this description.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

Claims (7)

1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 30% by weight of the compound of Formula 4, Compound 1 of Formula 5 ~ 70% by weight, and terephthalate derivative mixture comprising 1 to 80% by weight of the compound of Formula 6; And a phthalate compound represented by the following Chemical Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound is 5 to 95:95 to 5. [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The method of claim 1, The composite plasticizer composition, 1 to 10% by weight of the compound of Formula 1, 5 to 15% by weight of the compound of Formula 2, 10 to 40% by weight of the compound of Formula 3, 5 to 15% by weight of the compound of Formula 4, 10 to 30% by weight of the compound of Formula 5, And 10 to 40 wt% of a compound of Formula 6; And a phthalate compound represented by Chemical Formula 7, wherein the weight ratio of the terephthalate derivative mixture to the phthalate compound is 20 to 40:80 to 60. A polymer resin composition comprising the composite plasticizer composition of any one of claims 1 and 2. The method of claim 3, wherein The composite plasticizer composition is added to 30 to 120 parts by weight based on 100 parts by weight of the polymer resin. The method of claim 3, wherein The polymer resin is any one or two or more selected from polyvinyl chloride resin, olefin resin, ABS resin, acrylic resin and polyester resin. Molded article prepared from the polymer resin composition of claim 3. a) synthesizing a terephthalate derivative mixture by reacting a reaction solution comprising 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and terephthalic acid; And b) mixing the synthesized terephthalate derivative mixture with a phthalate compound of Formula 7; Method for producing a composite plasticizer composition comprising a. [Formula 7]