KR20140046215A - Plasticizer, plasticizer composition, heat-resistant resin 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 the plasticizer is used for the heat-resistant resin composition: elongation remaining rate is increased, thereby improving aging resistance and thermal resistance; and tensile strength, elongation remaining rate, and heating weight reduction are improved before and after a heating process, thereby contributing to the increase of matter properties of a heat-resistant resin.

Description

Plasticizer, plasticizer composition, heat resistant resin composition and method for preparing the same {Plasticizer, plasticizer composition, heat-resistant resin composition, and method for preparing

The present invention relates to a plasticizer, a plasticizer composition, a heat-resistant resin composition and a method for producing the same, more specifically, when used as a plasticizer of the heat-resistant resin composition, the elongation residual ratio is improved to improve aging resistance and heat resistance, tensile strength and tension before and after heating The present invention relates to a plasticizer, a plasticizer composition, a heat resistant resin composition, and a method for producing the same, which are excellent in residual ratio, heating loss, and the like, which may contribute to improvement of physical properties of the heat resistant resin.

Typically, plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters. 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 manufacture wires, automobile seats, etc. requiring heat resistance properties, it is necessary to use a suitable plasticizer according to the heat resistance grade of UL.

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

At this time, the type of plasticizer is different depending on the heat resistance grade, usually 80 to 90 ℃ class using dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP) and the like, 105 Trioctyl trimellitate (TOTM), triisononyl trimellitate (TINTM), etc. are used for the grade C.

However, these plasticizers have the disadvantage that they have heat resistance but poor compatibility.

In addition, the resin applied according to the heat resistance grade of the wire is also different, and low-cost PVC is mainly used for products below 105 ° C, and polyolefins such as polyethylene (PE) and thermoplastic elastomers (TPE) are used for 105-150 ° C products. Mainly used.

In the production of the double polyethylene compound, since polyethylene itself does not have flame retardancy, a flame retardant must be added, unlike PVC, and a crosslinking agent is required for irradiation. That is, carbon black is added to polyethylene, a plasticizer, a crosslinking agent, a flame retardant, and the like is added, followed by stirring to prepare a compound 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 including the same.

Accordingly, the inventors of the present invention continue to study the heat-resistant plasticizer terephthalate having an alkyl group having 10 carbon atoms (hereinafter referred to as C10) to overcome the weak heat resistance of the terephthalate plasticizer having an alkyl group having 8 carbon atoms (hereinafter referred to as C8). The formulation of the compound has resulted in the identification of plasticizer compositions that can improve up to poor compatibility that has arisen due to structural limitations and has led to the completion of the present invention.

That is, it is an object of the present invention to provide a plasticizer capable of improving physical properties such as heat resistance and compatibility required by a heat resistant compound when used as a plasticizer of a heat resistant resin composition, a composition thereof, a heat resistant resin composition including the same, and a method of manufacturing the same.

According to this invention, the terephthalate plasticizer represented by following formula 1 is provided.

[Chemical Formula 1]

Moreover, according to this invention, as a plasticizer composition,

5 to 60 wt% of the aforementioned terephthalate plasticizer;

0.1 to 50 wt% of a terephthalate compound represented by Formula 2; And

It provides a plasticizer composition comprising a; 30 to 85 wt% of a terephthalate compound represented by the following formula 3.

(2)

(3)

Further, according to the present invention,

Mixing terephthalic acid under a mixed solvent of alcohol;

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

Removing unreacted alcohol and neutralizing unreacted acid; And

Distilling under reduced pressure 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; To provide a method for producing a plasticizer composition.

[Chemical Formula 1]

 (2)

(3)

Further, according to the present invention,

Heat resistance characterized in that it comprises 5 to 100 parts by weight of the above-described plasticizer or plasticizer composition based on 100 parts by weight of the resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. It provides a resin composition.

Hereinafter, the present invention will be described in detail.

First, in this invention, as a plasticizer, it has a technical characteristic in providing the terephthalate plasticizer represented by following formula (1).

[Chemical Formula 1]

In this case, when the carbon atoms constituting the plasticizer are carbon atoms 8, 9 and the like instead of carbon atoms 8 and 10 suggested in the present invention, there are poor effects in terms of physical properties such as aging resistance, heat resistance, tensile strength, tensile residual ratio, elongation residual ratio and heating loss. It is confirmed.

In the present invention, as a plasticizer composition,

5 to 60 wt% of the aforementioned plasticizer;

0.1 to 50 wt% of a terephthalate compound represented by Formula 2; And

Characterized in that it comprises a; 30 to 85 wt% terephthalate compound represented by the following formula 3.

 (2)

(3)

In addition, when the carbon atoms constituting the plasticizer composition are carbon atoms 8, 9 and the like, which are not carbon atoms 8 and 10 presented in the present invention, they are poor in terms of physical properties such as aging resistance, heat resistance, tensile strength, tensile residual ratio, elongation residual ratio and heating loss. The effect is confirmed.

At this time, when the blending amount of the terephthalate compound represented by Formula 1 is less than 5 wt% based on the total weight of the composition, the absorption rate of the resin is poor and the hardness is high, and when it exceeds 60 wt%, it is not preferable in terms of elongation residual ratio and heating loss. . In one example, the compounding amount of the terephthalate compound may be in the range of 1 to 35 wt%.

In addition, the amount of terephthalate represented by the formula (2) is less than 0.1 wt% based on the total weight of the composition is poor in the absorption rate of the resin, if it exceeds 50 wt% is not preferable in terms of migration loss (migration loss). In one example, the terephthalate compounding amount may be in the range of 1 to 35 wt%.

In addition, the amount of terephthalate represented by Formula 3 is less than 30 wt% based on the total weight of the composition, the effect of improving heat resistance is insignificant, and when it exceeds 85 wt%, it is not preferable in terms of migration loss. In one example, the compounding amount of the terephthalate may be in the range of 64 to 80 wt%.

These plasticizer compositions may be prepared by blending the respective components, or may be used as a mixture itself blended through an esterification reaction with terephthalic acid using an appropriate alcohol mixture.

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

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

The catalyst is then added to the mixture and reacted under a nitrogen atmosphere (second step). The reaction alcohol is then removed and the unreacted acid is neutralized (third step).

Further, distillation under reduced pressure, dehydration and filtration yielded a terephthalate composition (fourth step).

At this time, the alcohol mixed solvent used in the first step is 2-propylheptyl alcohol, 4-methyl-2-propyl-1-hexyl alcohol, 5-methyl-2-propyl-1-hexyl alcohol, normaldecyl alcohol, and isodecyl It is characterized in that the mixture of C10 alcohol selected from alcohol and C8 alcohol selected from 2-ethylhexyl alcohol and normal octyl alcohol. This is a terephthalate-based composition obtained by adding a C10 alcohol having a high molecular weight in consideration of the poor heat resistance when using a terephthalate-based plasticizer obtained by using a C8 alcohol that imparts the appropriate molecular weight and physical properties of the plasticizer. This compatibility makes it possible to have an improved synergistic effect.

Specifically, the alcohol mixed solvent comprises 10 to 90 wt% of a C10 alcohol such as 2-propylheptyl alcohol and 10 to 90 wt% of a C8 alcohol such as 2-ethylhexyl alcohol to constitute a terephthalate-based composition obtained. 5 to 60 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) are preferable.

At this time, the terephthalic acid may also be used in combination with carboxylic acid, polycarboxylic acid or anhydride thereof. In particular, the terephthalic acid may shorten the reaction time by the average particle diameter of 30 to 100 ㎛ by wet milling, at this time can quickly reach the desired average particle size distribution by using a high speed wet milling device.

In this case, by adjusting the molar ratio of the starting material alcohol, it is possible to control the content ratio of the products.

In addition, the catalyst to be used is a titanate-based catalyst such as tetra-isopropyl titanate and tetra-normal butyl titanate. For reference, when the acid catalyst is used, there are more side reactions than the organometallic catalyst, the discoloration of the product is easy, and the corrosion of the facility may be caused.

At this time, the reaction temperature may be in the range of 180 to 280 ℃.

The terephthalate composition obtained in this way is 5 to 60 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 of the terephthalate compound represented by the formula (3). wt%, may be configured to include.

Specifically, 1 to 35 wt% of the terephthalate compound represented by Formula 1, 1 to 35 wt% of the terephthalate compound represented by Formula 2, and 64 to 80 wt% of the terephthalate compound represented by Formula 3, Can be.

Examples of the plasticizer composition include, but are not limited to, the plasticizer composition based on 100 parts by weight of a resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. It can be included in 100 parts by weight to provide a heat-resistant resin composition.

Meanwhile, only the terephthalate compound having Formula 1 in the terephthalate composition may be separated and applied as a plasticizer.

Specifically, with respect to 100 parts by weight of the resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, thermoplastic elastomer, including 5 to 100 parts by weight of a plasticizer having the formula (1) A resin composition can be provided.

The heat resistant resin composition may include one or more additives such as fillers such as 0.5 to 7 parts by weight of stabilizer, 0.5 to 3 parts by weight of lubricant, other plasticizers, flame retardants, crosslinking agents, and carbon black.

In this case, the heat-resistant resin composition may be applied as a compound prescription or a sheet prescription, and the heat-resistant resin composition may be applied to manufacture heat-resistant products such as wires, automobile interiors, films, sheets, or tubes, as identified in the following examples. Heating loss, heat resistance and compatibility can be provided.

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

Hereinafter, an Example is given and this invention is demonstrated concretely. However, the following examples are only examples of the present invention and are not meant to limit the present invention thereto.

< Example  1>

To a mixed reaction mixture of 2.65 mol of terephthalic acid, 1.59 mol of 2-ethylhexanol, and 6.36 mol of 2-propylheptanol in a 5-necked round flask equipped with a temperature sensor, a mechanical stirrer, a condenser, a decantor and a nitrogen injector. 0.0056 mol of tetraisopropyl titanate was added as a reaction catalyst and the reaction was carried out at 235 ° C. for 4 hours.

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

The obtained plasticizer was analyzed by a GC-Mass analyzer, it was confirmed that the compound having the above formulas 1,2,3, and the weight ratio was found to be 25: 2: 73.

< Example  2>

In Example 1, the same process was repeated except that a mixed reaction mixture of 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 GC-Mass analyzer, and it was confirmed that the compound represented by the formula (1) was the owner. Specifically, it was confirmed that the compounds having Formulas 1,2 and 3 each consisted of a weight ratio of 52: 2: 46.

< Comparative Example  1>

In Example 1, 2.65 mol of phthalic anhydride instead of terephthalic acid and 7.95 mol of isononyl alcohol instead of 2-ethylhexanol and 2-propylheptanol were mixed 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 reacted at 220 ° C. for 5 hours.

< Comparative Example  3>

In Example 1, 2.65 mol of phthalic anhydride 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 for 9 hours at a temperature of 220 ° C. under 0.056 mol of tetraisopropyl titanate, followed by excess of reduced pressure. Alcohol was extracted and removed.

It was neutralized with soda ash, washed with water once, heated under reduced pressure, dehydrated, and filtered by filtration to obtain a plasticizer composition.

The obtained plasticizer was analyzed by GC-Mass analyzer, and found to be 10% of diethylhexyl terephthalate, 54% of ethylhexyl isononyl terephthalate, and 36% of diisononyl terephthalate.

For fabrication of the specimens using Examples 1-2 and Comparative Examples 1-4 as plasticizers, 50 parts by weight of plasticizer, 3 parts by weight of calcium-zinc stabilizer (LTX-620S), stearic acid, and 100 parts by weight of PVC, with reference to ASTM D 638. After blending 0.2 parts by weight, the roll mill was operated at 165 ° C. for 3 minutes to produce a 5 mm sheet, and the press work was performed at 185 ° C. for 3 minutes, preheated 3 minutes, and cooled for 3 minutes. Several dumbbell-shaped specimens of type "C") were produced.

Each sheet was used to perform the following physical property tests and the results are summarized in Table 1 below.

<Test items>

1) Hardness ( ASTMD785 ): Hardness tester ("C" type) After the needle was lowered completely 10 seconds after the hardness value was read. The hardness was tested on three specimens for each specimen and then the average value was calculated.

2) The tensile strength , Elongation  [ ASTM D638 ]:

After pulling the cross head speed (200 mm / min) using the UTM Tersus instrument was measured the elongation and tensile strength at the point where the specimen is cut. The tensile strength (kgf / cm ² ) was calculated by load value (kgf) / thickness (cm) × width (cm), and elongation (%) was calculated as extension / initial length × 100.

3) seal Residual rate :

After standing for 168 hr at 100 ℃ using a gear oven, the cross head speed to 200 mm / min using a UTM test device by the ASTM D638 method, and then tensile strength (kgf / cm ² ) Was calculated as load value (kgf) / thickness (cm) x width (cm). The result of ASTM D638 method at room temperature was divided by the result after heating to obtain a% value.

4) height Residual rate :

After 168 hr at 100 ° C using a gear oven, the cross head speed was pulled to 200 mm / min using UTM, a test instrument by the ASTM D638 method, and the point where the specimen was cut was measured. Post elongation (%) was calculated as extension / initial length × 100. The result of ASTM D638 method at room temperature was divided by the result after heating to obtain a% value.

5) Improvability:

Initial weights (Wi) were measured for each specimen to four decimal places. Put the sheet (3cm x 3 cm) between the polystyrene plates in an oven at 80 ℃, and leave it for 72 hours under a load of 1kg, take out the specimen and store it in a thermostat for at least 4 hours, then measure the weight (Wq) of the specimen In addition, the amount of shift calculation was (Wi-Wq) / Wi x 100.

6) Heating loss:

Initial weights (Wi) were measured for each specimen to four decimal places. The specimen was fixed in an oven at 121 ° C. using a clamp, and after 72 hours the specimen was removed and stored in a thermostat chamber for at least 4 hours. The weight of the specimen (Wo) was measured and the heating loss was calculated by (Wi-Wo) / Wi x 100 was set.

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 (kg / 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 Residual (%) 100 98 103.4 101 101 98.9 Elongation Retention (%) 84 75 74.6 87 78 75.5 Migratory resistance (%) 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, in Example 1-2, it can be seen that the heat resistance is excellent. Specifically, Example 1-2 has better heat resistance of the heating loss portion than Comparative Examples 3 and 4, and as a result of comparing Example 1-2 with Comparative Example 1-2, elongation residual ratio, migration resistance, heating loss. This improvement could be identified.

Claims (14)

Terephthalate plasticizer represented by following formula (1).
[Chemical Formula 1]

As a plasticizer composition,
5 to 60 wt% of the plasticizer of claim 1;
0.1 to 50 wt% of a terephthalate compound represented by Formula 2; And
30 to 85 wt% of a terephthalate compound represented by the following Formula 3; comprising a plasticizer composition.
(2)

(3)

3. The method of claim 2,
1 to 35 wt% of the plasticizer of claim 1; 1 to 35 wt% terephthalate compound represented by Formula 2; And 64 to 80 wt% of a terephthalate compound represented by Formula 3 below.
Mixing terephthalic acid under 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
Distilling under reduced pressure 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; The manufacturing method of a plasticizer composition.
[Chemical Formula 1]

(2)

(3)

5. The method of claim 4,
The alcohol mixed solvent is a C10 alcohol selected from 2-propylheptyl alcohol, 4-methyl-2-propyl-1-hexyl alcohol, 5-methyl-2-propyl-1-hexyl alcohol, normaldecyl alcohol, and isodecyl alcohol, And a mixture of C8 alcohol selected from 2-ethylhexyl alcohol and normal octyl alcohol.
6. The method of claim 5,
The alcohol mixed solvent is a method for producing a plasticizer composition, characterized in that consisting of 10 to 90 wt% C10 alcohol, and 90 to 10 wt% C8 alcohol. 5. The method of claim 4,
The catalyst is a method for producing a plasticizer composition, characterized in that the organometallic catalyst selected from tetra-isopropyl titanate and tetra- normal butyl titanate.
5. The method of claim 4,
The terephthalate composition includes 5 to 60 wt% of a terephthalate compound represented by Formula 1, 0.1 to 50 wt% of a terephthalate compound represented by Formula 2, and 30 to 85 wt% of a terephthalate compound represented by Formula 3, The manufacturing method of a plasticizer composition characterized by the above-mentioned.
9. The method of claim 8,
The terephthalate composition comprises 1 to 35 wt% of terephthalate compound represented by Formula 1, 1 to 35 wt% of terephthalate compound represented by Formula 2, and 64 to 80 wt% of terephthalate compound represented by Formula 3, A method for producing a plasticizer composition, characterized in that. 5. The method of claim 4,
Furthermore, separating the terephthalate compound having the formula 1 in the terephthalate composition; Including, plasticizer manufacturing method.
[Chemical Formula 1]

A heat resistant resin comprising 5 to 100 parts by weight of the plasticizer according to claim 1 with respect to 100 parts by weight of the heat resistant resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. Composition.
Heat resistance characterized in that it comprises 5 to 100 parts by weight of the plasticizer composition according to claim 2 with respect to 100 parts by weight of the heat resistant resin selected from ethylene vinyl acetate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, and thermoplastic elastomer. Resin composition.
13. The method according to claim 11 or 12,
The heat-resistant resin composition is a heat-resistant resin composition characterized in that applied to the compound prescription or sheet prescription.
13. The method according to claim 11 or 12,
The said heat resistant resin composition is applied to manufacture of an electric wire, an automotive interior material, a film, a sheet, or a tube, The heat resistant resin composition characterized by the above-mentioned.