KR101569560B1 - Plasticizer composition, method for preparing thereof, and heat-resistant resin composition - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a plasticizer composition, a method of producing the same, and a heat-resistant resin composition. When used as a plasticizer of a heat-resistant resin composition, the composition exhibits excellent resistance to aging and heat loss and improved aging resistance and heat resistance. Can contribute to improvement of the physical properties of the heat resistant resin.

Description

Plasticizer composition, method for preparation thereof, and heat-resistant resin composition [0002]

More specifically, the present invention relates to a plasticizer composition, a method of manufacturing the same, and a heat-resistant resin composition. More specifically, the present invention relates to a plasticizer for a heat-resistant resin composition having improved elongation percentage when used as a plasticizer, And can contribute to improvement of the physical properties of the heat-resistant resin, a production method thereof, and a heat-resistant resin composition.

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, a suitable plasticizer should be used according to the UL heat resistance rating in order to produce wires and automobile interior materials which require heat resistance as physical properties.

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 are disadvantageous in that they have heat resistance and poor compatibility.

In addition, resins applied to wires are different according to the heat resistance grade. Polyolefins such as polyethylene (PE) and thermoplastic elastomers (TPE) are used for 105 ℃ to 150 ℃ products. Mainly used.

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.

Accordingly, the inventors of the present invention have been studying a heat resistant plasticizer, and in order to compensate for the weak heat resistance of an alcohol having an alkyl group having 8 carbon atoms (hereinafter referred to as C8), an alkyl group having 10 more carbon atoms (hereinafter referred to as C10) And it has been found that the poor compatibility caused by the structural limitations of terephthalic acid can be improved by mixing a phthalate plasticizer. Thus, the present invention has been accomplished.

That is, an object of the present invention is to provide a plasticizer composition capable of improving the poor compatibility caused by structural limitations when the C10 terephthalate compound is introduced to overcome the poor heat resistance of the C8 terephthalate plasticizer and mixed with dipropylheptyl phthalate And a manufacturing method thereof.

According to the present invention,

A terephthalate compound represented by the formula (1); A terephthalate compound represented by the formula (2); A terephthalate compound represented by the formula (3); And a phthalate compound represented by the general formula (4); ≪ / RTI >

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

Further, according to the present invention,

Mixing terephthalic acid in an alcohol mixed solvent;

Adding a catalyst to the mixture and reacting in a nitrogen atmosphere;

Removing unreacted alcohol and neutralizing the unreacted acid;

(1), a terephthalate compound represented by the formula (2), and a terephthalate compound represented by the formula (3) to obtain a terephthalate composition; And

Mixing the terephthalate composition with the phthalate compound of Formula 4; ≪ RTI ID = 0.0 > a < / RTI > plasticizer composition.

Further, according to the present invention,

Wherein the plasticizer composition is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of a resin selected from vinyl chloride resin, polyethylene, polypropylene, polystyrene and polyurethane.

Hereinafter, the present invention will be described in detail.

First, in the present invention, as the plasticizer composition, a terephthalate compound represented by Chemical Formula 1; A terephthalate compound represented by the formula (2); A terephthalate compound represented by the formula (3); And a phthalate compound represented by the general formula (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

Wherein the terephthalate composition comprises 0.1 to 50 wt% of the terephthalate compound represented by Formula 1, 0.1 to 50 wt% of the terephthalate compound represented by Formula 2, and 30 to 85 wt% of the terephthalate compound represented by Formula 3 The total amount is 100% by weight, and the phthalate compound represented by the general formula (4) is contained in an amount of 0.1 to 50% by weight.

For example, the terephthalate composition comprises 10 to 40 wt% of the terephthalate compound represented by Formula 1, 0.1 to 25 wt% of the terephthalate compound represented by Formula 2, and 40 to 70 wt% of the terephthalate compound represented by Formula 3, , And the phthalate compound represented by the general formula (4) may be contained in an amount of 10 to 30% by weight.

When the number of carbon atoms constituting the plasticizer composition is not 8, 10, or 8, such as 8,9, or 9, which is the present invention, a poor effect is confirmed in terms of physical properties such as aging resistance, heat resistance and weight loss.

If the blending amount of the terephthalate compound represented by the formula (1) is less than 0.1 wt% based on the total weight of the composition, the tensile strength and the elongation percentage become poor. When the blending amount exceeds 50 wt%, the tear resistance and the heating loss are poor. For example, the compounding amount of the terephthalate compound may be in the range of 10 to 40 wt%.

If the amount of terephthalate represented by the formula (2) is less than 0.1 wt% based on the total weight of the composition, physical properties related to workability such as an absorption rate and a melting rate become poor. When the content exceeds 50 wt% Heat resistance is poor. For example, the amount of terephthalate may be in the range of 0.1 to 25 wt%.

When the amount of terephthalate represented by the general formula (3) is less than 30 wt% based on the total weight of the composition, heat resistance such as resistance to migration and heating loss is poor, and 85 If it exceeds the wt%, the hardness becomes high, and the physical properties related to the workability such as the absorption rate and the melting rate become very low. For example, the blending amount of the terephthalate may be in the range of 40 to 70 wt%.

Further, the phthalate compound represented by the general formula (4) can be used in place of dioctyl phthalate, diethylhexyl phthalate and diisononyl phthalate, As described in the following examples, when used alone, it has a disadvantage in that it has poor heat resistance such as heat resistance and heat loss. On the other hand, when it is blended with the terephthalate compound of the above-mentioned formula 1, 2 or 3, And it was confirmed that they showed a synergistic effect in terms of compatibility.

The amount of the phthalate compound is in the range of 0.1 to 50 wt% based on 100 wt% of the total amount of the terephthalate compound represented by the formula (1) If the amount is less than 0.1 wt%, the effect of improving the compatibility is insignificant. If the amount exceeds 50 wt%, the improvement effect is not excellent. For example, the amount of the phthalate compound may be in the range of 10 to 30 wt%.

The composition of the present invention is applied to a resin selected from the group consisting of ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer to manufacture heat resistant articles such as wire, automobile interior material, film, And the like.

The plasticizer composition of the present invention is not limited thereto, but can be obtained simply and efficiently by the following production 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 and dehydrated and filtered to obtain a terephthalate composition comprising the terephthalate compound represented by the general formula (1), (2) and (3) (Step 4).

The phthalate compound represented by Chemical Formula 4 is mixed with the terephthalate composition thus obtained (Step 5).

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 a terephthalate plasticizer obtained by using a C8 alcohol which gives an appropriate molecular weight and physical properties of a plasticizer is used as a plasticizer for a heat resistant resin, considering the fact that the heat resistance is weak, a C10 alcohol having a high molecular weight is added to increase the heat resistance Respectively.

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

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

The catalyst used in the second step is a titania-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 in this way contains 0.1 to 50 wt% of the terephthalate compound represented by the formula (1), 0.1 to 50 wt% of the terephthalate compound represented by the formula (2), and 30 to 85 wt%, < / RTI >

Specifically, it comprises 10 to 40 wt% of the terephthalate compound represented by the formula (1), 0.1 to 25 wt% of the terephthalate compound represented by the formula (2) and 40 to 70 wt% of the terephthalate compound represented by the formula .

The fifth step of mixing the terephthalate composition obtained in the fourth step with dipropylheptyl phthalate may include adding 0.1 to 50 wt% of diphenylheptyl phthalate to 100 wt% of the total amount of the terephthalate composition, for example, 10 to 30 wt% .

The plasticizer composition thus obtained is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of the heat-resistant resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane and thermoplastic elastomer to obtain a heat- .

The heat-resistant resin composition may contain at least one additive selected from plasticizers, flame retardants, crosslinking agents, heat stabilizers, and fillers such as carbon black, if necessary, and may be applied in a compound or sheet form.

The heat-resistant resin composition is characterized by providing heat loss, heat resistance and compatibility so as to be applied to wire, automobile interior material, film, sheet, or tube manufacturing, as described in the following examples.

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>

2.65 mol of terephthalic acid, 1.59 mol of 2-ethylhexanol and 6.36 mol of 2-propylheptanol were reacted at a temperature of 235 DEG C under 0.056 mol of tetraisopropyl titanate for 4 hours, and then excess alcohol was extracted and removed under reduced pressure .

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, and as a result, it was confirmed that the compound was composed of compounds having the following general formulas (1), (2) and (3). In addition, it was confirmed that the weight ratio of Formula 1: Formula 2: Formula 3 was 25: 2: 73.

[Chemical Formula 1]

(2)

(3)

After the plasticizer of the above composition was synthesized, the compound of Chemical Formula 4 was added to the mixture so as to have a weight of 10 wt%.

[Chemical Formula 4]

< Example  2>

In Example 1, the same process was repeated except that the compound of Formula 4 was added so that the weight of the compound of Formula 4 was 30 wt%.

< Comparative Example  1>

In Example 1, the same process was repeated except that the compound of Formula 4 was added so as to have a weight of 60 wt% after mixing.

< Comparative Example  2>

In Example 1, the same process was repeated except that the compound of Formula 4 was not added.

< Comparative Example  3>

2.65 mol of phthalic anhydride and 8 mol of 2-propylheptanol were reacted at a temperature of 220 ° C for 3.5 hours in 0.056 mol of tetraisopropyl titanate, and the excess alcohol was extracted and removed under reduced pressure.

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.

< Comparative Example  4>

2.65 mol of terephthalic acid, 4 mol of 2-ethylhexanol and 4 mol of 2-propylheptanol were reacted at a temperature of 220 ° C under 0.056 mol of tetraisopropyl titanate for 9 hours, and then excess alcohol was extracted and removed under reduced pressure .

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.

< Comparative Example  5>

2.65 mol of phthalic anhydride and 8 mol of isodecanol were reacted in 0.056 mol of tetraisopropyl titanate at a temperature of 235 DEG C for 5 hours and then the excess alcohol was extracted and removed under reduced pressure.

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.

With respect to 100 parts by weight of PVC, 80 parts by weight of a plasticizer, 3 parts by weight of epoxidized soybean oil, and 2.5 parts by weight of a Ba-Zn stabilizer were added to 100 parts by weight of PVC according to ASTM D 638, And the roll mill was operated at 160 캜 for 4 minutes to prepare a 5 mm sheet. Then, a 1 mm sheet was produced at 180 캜 for 3 minutes (Low P) / 2 minutes and 30 seconds (High P), respectively.

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 10 seconds after the needle was completely lowered was read. The hardness was tested for three specimens for each specimen and the mean value was calculated.

2) The 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 (kgf) / thickness (cm) x width (cm) and elongation (%) was calculated as extension / initial length x 100.

3) Inner planet:

The initial weight (Wi) was measured to 4 decimal places for each specimen. Put sheets (3 cm x 3 cm) between polystyrene plates in an oven at 80 ° C, leave for 72 hours under a load of 1 kg, remove the specimens, store them for longer than 4 hours in a thermostatic chamber, measure the weight (Wq) (Wi-Wq) / Wi x 100, respectively.

4) Seat heating loss:

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

5) Plasticizer absorption rate:

200 g of plasticizer was rotated at 60 DEG C at 77 DEG C to 400 g of PVC and the time of absorption was measured.

division Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Properties Hardness 74.5 73 72.5 76.5 68 68 71 The tensile strength
(kg / cm2) 159 157 154 160 152 169 152 Elongation (%) 402 400 398 402 396 403 392 Inner planet (%) 0.76 0.78 0.85 0.75 0.88 1.05 0.74 Heat loss (%) 1.40 1.49 1.89 1.36 2.21 3.23 1.35 Absorption rate (sec) 610 590 570 740 544 470 525

As can be seen from the results of Table 1, it can be seen that Example 1-2 has excellent heat resistance and compatibility. Specifically, in Example 1-2, the heat resistance of the heat-shrinkable portion was superior to that of Comparative Examples 3 and 4, and the performance was excellent in tensile strength and elongation as compared with Comparative Example 5. Further, as a result of comparison between Example 1-2 and Comparative Example 2, it was confirmed that the addition of the compound of Formula 4 improved the compatibility.

Claims (14)

10 to 40 wt% of a terephthalate compound represented by the following formula (1);
0.1 to 25 wt% of a terephthalate compound represented by the following formula (2); And
And 40 to 70 wt% of a terephthalate compound represented by the following formula (3)
Wherein the plasticizer composition comprises 10 to 30% by weight of a phthalate compound represented by the following formula (4) based on 100% by weight of the total of the terephthalate compounds represented by the general formulas (1) to (3).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

delete delete delete Mixing terephthalic acid in a mixed solvent of C ₁₀ alcohol and C ₈ alcohol;
Adding a catalyst to the mixture and reacting in a nitrogen atmosphere;
Removing unreacted alcohol and neutralizing the unreacted acid;
(1), a terephthalate compound represented by the formula (2), and a terephthalate compound represented by the formula (3) to obtain a terephthalate composition; And
Mixing the terephthalate composition with the phthalate compound of Formula 4; &Lt; / RTI &gt;
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

6. The method of claim 5,
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 according to claim 6,
Wherein the alcohol mixture solvent comprises 50 to 90 wt% of C ₁₀ alcohol and 10 to 50 wt% of C8 alcohol.
6. The method of claim 5,
Wherein the catalyst is an organometallic catalyst selected from the group consisting of tetraisopropyl titanate and tetranormal butyl titanate.
delete 6. The method of claim 5,
The terephthalate composition comprises 10 to 40 wt% of the terephthalate compound represented by the formula (1), 0.1 to 25 wt% of the terephthalate compound represented by the formula (2) and 40 to 70 wt% of the terephthalate compound represented by the formula &Lt; / RTI &gt; wherein the plasticizer composition for PVC is prepared.
6. The method of claim 5,
Wherein the step of mixing the terephthalate composition with dipropylheptyl phthalate comprises mixing 10 to 30 wt% of diphenylheptyl phthalate in a total amount of 100 wt% of the terephthalate composition.
100 parts by weight of a polyvinyl chloride resin; And
A heat-resistant resin composition comprising 5 to 100 parts by weight of the plasticizer composition for PVC according to claim 1, based on 100 parts by weight of the resin.
13. The method of claim 12,
Wherein the heat-resistant resin composition is applied as a compound formulation or a sheet formulation.
14. The method of claim 13,
Wherein the heat-resistant resin composition is applied to the production of electric wire, automobile interior material, film, sheet or tube.