KR20180133827A - Plasticizer composition and method for preparing thereof - Google Patents

Abstract

The present invention relates to a plasticizer, a plasticizer composition, a heat-resistant resin composition, and a production method thereof. When used as the plasticizer in the heat-resistant resin composition, it is possible to improve elongation retention rate, thereby enhancing aging resistance and heat resistance. Owing to excellent heat loss, tensile retention rate, and tensile strength before and after heating, it is possible to bring improvement in physical properties in the heat-resistant resin.

Description

Plasticizer composition and method for preparing the same

More particularly, the present invention relates to a plasticizer composition and a process for producing the same, and more particularly to a plasticizer composition for use in a heat-resistant resin composition, which has an improved elongation percentage when used as a plasticizer to improve the resistance to aging and heat resistance and the tensile strength, And which can contribute to improvement of physical properties of a heat-resistant resin and a process for producing the same.

Typically, the plasticizer reacts with the polycarboxylic acid, such as phthalic acid and adipic acid, to form the corresponding ester. Commercially important examples include adipates of C8, C9 and C10 alcohols, such as di (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate; And phthalates of C8, C9 and C10 alcohols such as di (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate.

On the other hand, in order to produce electric wires and automobile sheets which require heat resistance as physical properties, a suitable plasticizer should be used according to UL heat resistance grade.

For example, in the case of PVC compound for UL wire, plasticizer, filler, flame retardant, heat stabilizer, etc. are added to PVC resin according to tensile strength, elongation and cold resistance which are required in UL wire standard.

(DOP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP) or the like is used in the range of 80 to 90 ° C., ° C, trioctyltrimellitate (TOTM), triisononyl trimellitate (TINTM) and the like are used.

However, these plasticizers have a disadvantage that they have poor heat resistance and poor compatibility.

In addition, resins applied to wires are different depending on the heat resistance grade of the wires. Polyolefins such as polyethylene (PE) and thermoplastic elastomers (TPE) are used in 105 to 150 ° C products. .

Since polyethylene itself does not have flame retardancy at the time of manufacture of the double polyethylene compound, a flame retardant must be added unlike PVC and a cross-linking agent for irradiation is required. That is, a plasticizer, a cross-linking agent, a flame retardant and the like are put into polyethylene and carbon black is mixed and stirred, and the compound is produced through an injection process.

Therefore, there is still a need for a plasticizer having excellent heat resistance and excellent compatibility (workability) and a heat-resistant resin composition containing the same.

The present inventors having (hereinafter referred to as, C ₁₀₎ having 8 alkyl group (hereinafter, C ₈ quot;) terephthalate having a carbon number of 10 in alkyl group to overcome the poor heat resistance of the plasticizer having a while trying to continue the study for heat resistance plasticizer The inventors of the present invention have completed the present invention by confirming a plasticizer composition capable of improving the compatibility of the terephthalate compound to poor compatibility caused by structural limitations.

That is, an object of the present invention is to provide a plasticizer, a composition thereof, and a heat-resistant resin composition containing the same that can improve physical properties such as heat resistance and compatibility required in a heat resistant compound when used as a plasticizer of a heat-

According to the present invention, there is provided a terephthalate plasticizer represented by the following formula (1).

[Chemical Formula 1]

Further, according to the present invention, as the plasticizer composition, 5 to 60% by weight of the above-mentioned terephthalate plasticizer; 0.1 to 50% by weight of a terephthalate compound represented by the following formula 2; And 30 to 85% by weight of a terephthalate compound represented by the following formula (3).

(2)

(3)

Further, according to the present invention, there is provided a method for producing terephthalic acid, comprising: mixing terephthalic acid in a mixed solvent of alcohol; Adding a catalyst to the mixture and reacting in a nitrogen atmosphere; Removing unreacted alcohol and neutralizing the unreacted acid; And dehydrating by vacuum distillation and filtering to obtain a terephthalate composition comprising a terephthalate compound represented by the following formula 1, a terephthalate compound represented by the following formula 2, and a terephthalate compound represented by the following formula 3: ≪ / RTI > by weight, based on the total weight of the composition.

[Chemical Formula 1]

(2)

(3)

Further, according to the present invention, 5 to 100 parts by weight of the above plasticizer or plasticizer composition is added to 100 parts by weight of a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer The present invention also provides a heat-resistant resin composition.

Hereinafter, the present invention will be described in detail.

First, the present invention has technical features in providing a terephthalate plasticizer represented by the following formula 1 as a plasticizer.

[Chemical Formula 1]

In this case, when the number of carbon atoms constituting the plasticizer is not 8, 10, or 8, the number of carbon atoms in the present invention is 8, 9, etc., there is a bad effect in terms of physical properties such as aging resistance, heat resistance, tensile strength, tensile residual rate, Is confirmed.

Further, in the present invention, as the plasticizer composition, 5 to 60% by weight of the above-mentioned plasticizer; 0.1 to 50% by weight of a terephthalate compound represented by the following formula 2; And 30 to 85% by weight of a terephthalate compound represented by the following formula (3).

(2)

(3)

Also, when the number of carbon atoms constituting the plasticizer composition is not 8, 10, or 8, such as 8,9 in the present invention, it is poor in physical properties such as aging resistance, heat resistance, tensile strength, tensile residual rate, The effect is confirmed.

If the blending amount of the terephthalate compound represented by the formula (1) is less than 5% by weight based on the total weight of the composition, the absorption rate of the resin is poor and the hardness is increased. When the blending amount exceeds 60% by weight, . For example, the compounding amount of the terephthalate compound may be in the range of 5 to 52 wt%, 5 to 35 wt%, or 1 to 35 wt%.

If the amount of terephthalate represented by the formula (2) is less than 0.1% by weight based on the total weight of the composition, the absorption rate of the resin is poor, while if it exceeds 50% by weight, it is not preferable from the viewpoint of migration loss. For example, the amount of the terephthalate compounded may be in the range of 1 to 35% by weight.

If the amount of terephthalate represented by the formula (3) is less than 30% by weight based on the total weight of the composition, the effect of improving the heat resistance is insignificant. If it exceeds 85% by weight, the terephthalate is not preferable from the viewpoint of migration loss. For example, the blending amount of the terephthalate may be in the range of 46 to 80 wt.%, 46 to 73 wt.%, Or 64 to 80 wt.%.

These plasticizer compositions may be prepared by mixing each component, or may be a mixture prepared by esterification with terephthalic acid using an appropriate alcohol mixture.

In one example, it can be obtained simply and efficiently by the following method:

First, terephthalic acid is mixed in an alcohol mixed solvent (the first step).

Then, the catalyst is added to the mixture and reacted in a nitrogen atmosphere (second step). Then, the reaction alcohol is removed and the unreacted acid is neutralized (Step 3).

Further distilled under reduced pressure, dehydrated and filtered to obtain a terephthalate composition (Step 4).

In this case, the alcoholic solvent used in the first step may include 2-propylheptyl alcohol, 4-methyl-2-propyl-1-hexyl alcohol, Is a mixture of a C10 alcohol selected from alcohols and a C8 alcohol selected from 2-ethylhexyl alcohol and n-octyl alcohol. This is because when the terephthalate plasticizer obtained by using C8 alcohol which gives appropriate molecular weight and physical properties of plasticizer is used as a plasticizer for heat resistant resin, terephthalate composition obtained by adding C10 alcohol having high molecular weight And this compatibility has an improved synergistic effect.

Specifically, the alcoholic solvent mixture is composed of 10 to 90% by weight of a C10 alcohol such as 2-propylheptyl alcohol, and 10 to 90% by weight of a C8 alcohol such as 2-ethylhexyl alcohol. The terephthalate- 5 to 60% by weight of the terephthalate compound represented by the formula (1), 0.1 to 50% by weight of the terephthalate compound represented by the formula (2) and 30 to 85% by weight of the terephthalate compound represented by the formula (3).

The terephthalic acid may be a carboxylic acid, a polycarboxylic acid or an anhydride thereof. Particularly, the terephthalic acid has a mean particle size of 30 to 100 mu m by wet grinding, which can shorten the reaction time. When the high-speed rotary wet grinding apparatus is used, the desired average particle size distribution can be quickly reached.

In this case, the content ratio of the products can be controlled by adjusting the molar ratio of the starting alcohol.

In addition, the catalyst used is a titanate-based catalyst such as tetra-isopropyl titanate or tetra-n-butyl titanate. For reference, the use of an acid catalyst results in a greater number of side reactions than organometallic catalysts, which can result in discoloration of the product and corrosion problems on the plant.

The reaction temperature may be in the range of 180 to 280 ° C.

The terephthalate composition obtained by this method is obtained by mixing 5 to 60% by weight of the terephthalate compound represented by the formula (1), 0.1 to 50% by weight of the terephthalate compound represented by the formula (2) and 30 to 85 % ≪ / RTI > by weight.

Specifically, it may comprise 5 to 52% by weight of the terephthalate compound represented by the formula (1), 1 to 35% by weight of the terephthalate compound represented by the formula (2) and 46 to 80% by weight of the terephthalate compound represented by the formula have.

Specifically, it may comprise 1 to 35% by weight of the terephthalate compound represented by the formula (1), 1 to 35% by weight of the terephthalate compound represented by the formula (2) and 64 to 80% by weight of the terephthalate compound represented by the formula have.

Application examples of the plasticizer composition include, but are not limited to, 100 parts by weight of a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer, 100 parts by weight of the heat-resistant resin composition.

On the other hand, only the terephthalate compound of Formula 1 may be separated from the terephthalate composition and applied as a plasticizer.

Specifically, it is preferable that the plasticizer having the formula 1 is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of a resin selected from the group consisting of ethylene-vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer, A resin composition can be provided.

The heat-resistant resin composition may contain at least one additive such as 0.5 to 7 parts by weight of a stabilizer, 0.5 to 3 parts by weight of a lubricant, and a filler such as a plasticizer, a flame retardant, a crosslinking agent, and a carbon black.

The heat-resistant resin composition can be applied to a compound formulation or a sheet formulation. The heat-resistant resin composition can be applied to the production of heat-resistant products such as wire, automobile interior material, film, sheet or tube, Heat loss, heat resistance, and compatibility.

According to the present invention, when used as a plasticizer of a heat-resistant resin composition, the elongation percentage is improved to improve the aging resistance and the heat resistance, and the tensile strength, the tensile residual rate, the heating loss and the like before and after heating can be improved to contribute to the improvement of the physical properties of the heat resistant resin.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the following examples are only illustrative of the present invention and do not limit the scope of the present invention.

≪ Example 1 >

A mixed round bottom flask equipped with a temperature sensor, mechanical stirrer, condenser, decanter and nitrogen inlet was charged with 2.65 mol of terephthalic acid, 1.59 mol of 2-ethylhexanol and 6.36 mol of 2-propylheptanol 0.0056 mol of tetraisopropyl titanate as a reaction catalyst was added and the reaction was carried out at 235 ° C for 4 hours.

After the reaction, the excess alcohol was extracted under reduced pressure, neutralized with water with soda ash and distilled water, dehydrated under reduced pressure distillation, and passed through a filter to obtain an ester plasticizer composition as a plasticizer composition of the present invention.

The obtained plasticizer was analyzed by a GC-Mass analyzer. As a result, it was confirmed that the compound was composed of the compound having the formula (1), (2), and (3), and the weight ratio thereof was confirmed to be 25: 2: 73.

≪ Example 2 >

In Example 1, the same process was repeated except that a mixed reaction product in which 2.65 mol of terephthalic acid, 4.11 mol of 2-ethylhexanol, and 3.84 mol of 2-propylheptanol was used.

The obtained plasticizer was analyzed by a GC-Mass analyzer, and it was confirmed that the compound represented by Chemical Formula 1 was the main component. Specifically, it was confirmed that the compounds having the general formulas (1), (2) and (3) were formed in a weight ratio of 52: 2: 46.

≪ Comparative Example 1 &

In Example 1, 2.65 mol of phthalic anhydride was used instead of terephthalic acid, and 7.95 mol of isononyl alcohol instead of 2-ethylhexanol and 2-propylheptanol were reacted at 240 ° C for 5 hours The same process was repeated except that.

≪ Comparative Example 2 &

In Example 1, the same process was repeated except that 2.65 mol of terephthalic acid and 7.95 mol of 2-propylheptanol were used and 2-ethylhexanol was not used and the reaction was conducted at 220 캜 for 5 hours.

≪ Comparative Example 3 &

In Example 1, 2.65 mol of phthalic anhydride was used instead of terephthalic acid, and 7.95 mol of isodecyl alcohol instead of 2-ethylhexanol and 2-propylheptanol were reacted at 220 ° C. for 5 hours The same process was repeated except that.

≪ Comparative Example 4 &

In Example 1, 2.65 mol of terephthalic acid, 5.29 mol of 2-ethylhexanol and 5.29 mol of 2-isononyl alcohol were reacted at a temperature of 220 캜 for 9 hours under 0.056 mol of tetraisopropyl titanate, Alcohol was extracted and removed.

Neutralized with soda ash, rinsed once with water, and then dehydrated by heating under reduced pressure. Then, the filter material was charged and filtered to obtain a plasticizer composition.

The obtained plasticizer was analyzed by a GC-Mass analyzer. As a result, it was confirmed that 10% of diethylhexyl terephthalate, 54% of ethylhexyl isononyl terephthalate, and 36% of diisononyl terephthalate.

As a test piece using the above-described Example 1-2 and Comparative Example 1-4 as a plasticizer, 50 parts by weight of a plasticizer, 3 parts by weight of a calcium-zinc stabilizer (LTX-620S), 100 parts by weight of stearic acid 0.2 mm in thickness and 0.2 mm in length. The roll mill was operated at 165 占 폚 for 3 minutes to prepare a 5 mm sheet. After the preheating for 3 minutes, the heating for 3 minutes and the cooling for 3 minutes at 185 占 폚, Several types of dumbbell specimens were made with type "C".

The following physical property tests were carried out using each sheet and the results are summarized in Table 1 below.

<Test items>

1) Hardness (ASTM D785)

Hardness tester ("C" type) The hardness value that appeared after 10 seconds was completely read. The hardness was tested for three specimens for each specimen and the mean value was calculated.

2) Tensile strength, elongation [ASTM D638]

The tensile strength and elongation at the point where the specimen was cut were measured after pulling the cross head speed at 200 mm / min using a UTM (teres machine). The calculation of the tensile strength (kgf / cm ² ) was calculated as load value (kgf) / thickness (cm) x width (cm) and elongation (%) was calculated as extension / initial length x 100.

3) Tensile Residue

After being left at 100 ° C for 168 hours using a gear oven, tensile strength (kgf / cm ² ) was obtained by pulling the cross head speed at 200 mm / min using UTM as a test instrument by ASTM D638 method, Was calculated as load value (kgf) / thickness (cm) x width (cm). The results of the ASTM D638 method at room temperature were divided by the results after heating to obtain% values.

4) Renal survival rate

The sample was allowed to stand at 100 ° C for 168 hours using a gear oven. The sample was pulled at a crosshead speed of 200 mm / min using a UTM test machine according to ASTM D638, and the point at which the sample was cut was measured The posterior elongation (%) was calculated as the estension / initial length x 100. The results of the ASTM D638 method at room temperature were divided by the results after heating to obtain% values.

5) Inner planet

The initial weight (Wi) was measured to 4 decimal places for each specimen. After placing the sheet (3 cm x 3 cm) between polystyrene plates in an oven at 80 ° C and leaving it for 72 hours under a load of 1 kg, remove the specimen, store it for more than 4 hours in a thermostat, (Wi-Wq) / Wi x 100, respectively.

6) Heat loss

The initial weight (Wi) was measured to 4 decimal places for each specimen. The specimen was held in a 121 ° C oven with a clamp, and after 72 hours, the specimen was taken out and stored in a thermostat for 4 hours or more. The weight (Wo) of the specimen was measured, 100.

division Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Properties Hardness 94.5 93.5 87.5 98.5 89 90 Room temperature Elongation (%) 200.0 198.6 171.6 215.3 193.5 181.8 Tensile strength (kgf / cm ² ) 285.7 240.0 256.8 218.9 251.1 275.1 heating
after Elongation (%) 199.7 193.9 177.6 218.4 196.5 179.8 The tensile strength
(kg / cm ² ) 204.4 182.1 191.8 193.2 196.1 207.8 Tensile Residue (%) 100 98 103.4 101 101 98.9 Renal survival rate (%) 84 75 74.6 87 78 75.5 Inner planet (%) 0.3 0.2 0.2 0.5 0.2 0.1 Heat loss (%) 1.4 3.7 5.3 0.5 4.4 3.9

As can be seen from the results of Table 1, it can be seen that Examples 1 and 2 have excellent heat resistance. Specifically, Examples 1 and 2 are superior to Comparative Examples 3 and 4 in heat resistance properties of the weight loss portion. Further, as a result of comparison between Examples 1 and 2 and Comparative Examples 1 and 2, the elongation percentage, Can be identified.

Claims (6)

5 to 60% by weight of a terephthalate compound represented by the following formula (1); 0.1 to 50% by weight of a terephthalate compound represented by the following formula (2); And 30 to 85% by weight of a terephthalate compound represented by the following formula (3):
[Chemical Formula 1]

(2)

(3)

The method according to claim 1,
5 to 60% by weight of the terephthalate compound represented by the formula (1); 1 to 35% by weight of a terephthalate compound represented by Formula 2; And 30 to 85% by weight of a terephthalate compound represented by the following general formula (3).
Mixing terephthalic acid in a mixed solvent of C ₈ alcohol and C ₁₀ alcohol;
Adding a catalyst to the mixture and reacting in a nitrogen atmosphere;
Removing unreacted alcohol and neutralizing the unreacted acid; And
Dehydrating and dehydrating by distillation under reduced pressure to obtain a plasticizer composition.
The method of claim 3,
The C ₁₀ alcohol is at least one selected from 2-propylheptyl alcohol, 4-methyl-2-propyl-1-hexyl alcohol, ,
Wherein the C ₈ alcohol is at least one selected from 2-ethylhexyl alcohol and n-octyl alcohol.
The method of claim 3,
Wherein the alcohol mixed solvent is composed of 10 to 90 wt% of C ₁₀ alcohol, and 90 to 10 wt% of C ₈ alcohol.
The method of claim 3,
Wherein the catalyst is an organometallic catalyst selected from tetra-isopropyl titanate and tetranormal butyl titanate.