KR20140018610A - Diphosphite-based antioxidant material and polymer resin composition including same - Google Patents

Abstract

The present invention relates to an diphosphite antioxidant and a polymer resin composition including the same, and the antioxidant is a diphosphite antioxidant represented by formula 1. [formula 1].

Description

Diphosphite-based antioxidant and polymer resin composition containing same {DIPHOSPHITE-BASED ANTIOXIDANT MATERIAL AND POLYMER RESIN COMPOSITION INCLUDING SAME}

The present disclosure provides a diphosphite-based antioxidant and a polymer resin composition comprising the same.

Plastic materials are inferior in properties such as heat resistance and flame retardancy compared to metal or ceramic materials, but they are widely used as industrial materials in household goods, automobiles, electrical, electronics, and industrial fields due to advantages such as light weight, design flexibility, and molding processability. .

However, the polymer resin constituting the plastic causes chemical changes, that is, oxidation reactions due to light, heat, pressure, shear force, etc. in the presence of oxygen. This oxidation reaction is a radical reaction, which causes mechanical problems of the polymer resin oil, or causes problems such as color change, gas and sunspot generation.

In the polymer resin constituting the plastic, hydrogen bonds present in the polymer resin are cleaved by the oxidation reaction by heat, oxygen, light, or the like to generate alcohol or peroxy radicals. The oxidation reaction may also be promoted when the residual catalyst or metal in the plastic comes into contact with the plastic. In particular, when thermal oxidation occurs, physical properties of the plastic itself change due to the cutting of the molecular chain (strength, molecular weight decrease, etc.), crosslinking (curing, gelling, elasticity reduction, coloring, etc.), thereby degrading or eliminating the original function. It becomes impossible.

For this reason, when forming plastics, only a few polymer resins are used, and a small amount of additives are additionally added in accordance with the application to supplement the properties thereof. Representative additives include lubricants, stabilizers, flame retardants, plasticizers, impact modifiers, pigments and the like. Stabilizers are used to eliminate or inhibit chemical degradation during the manufacture, processing and use of plastics and, depending on their function, can be divided into antioxidants, heat stabilizers, UV stabilizers and the like.

Among them, the antioxidant includes a primary antioxidant and a secondary antioxidant, and the primary antioxidant refers to a substance that functions as a radical scavenger that reacts with radicals generated in the polymer resin to stabilize the polymer resin. Phenolic and aromatic amines are typically used as primary antioxidants.

Secondary antioxidants serve to stabilize the polymer resin by removing oxygen atoms of the already oxidized polymer resin, and phosphite compounds and sulfur compounds are typically used.

Among these, phosphite is a substance in which a hydroperoxide formed by cleaving hydrogen bonds remaining in a polymer resin by heat, oxygen, and light is converted to alcohol and itself is converted into phosphate. Such phosphites are not colored and also serve to prevent coloring of phenolic stabilizers.

The use of these phosphites reduces the color development by phenolic stabilizers to protect the polymer from discoloration , and since phosphite acts as an antioxidant, the plastic itself can be broken by cross-linking, molecular chains, etc. The deterioration of physical properties can be suppressed . Commercially available phosphites include trisnonylphenylphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Can be mentioned.

Trisnonylphenyl phosphite (TNPP) is the most widely used substance, but it is considered to be a representative endocrine disruptor and has low degradability and high concentration characteristics. Because of its impact on humans and the environment, manufacturing, importation and use are restricted.

Tris- (2.4-di-tert-butylphenyl) phosphite has good hydrolytic stability, while not as effective as desired for color stability and melt-flow stabilization.

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is hygroscopic and has a problem in that there is no hydrolytic stability. When exposed to moisture for a period of time, they tend to clump and become sticky clumps.

The phosphite stabilizer is highly hydrolyzable to form phosphorous acid (Phosphorous acid), the stabilizer effect is reduced and may cause corrosion of the processing equipment.

Thus, to date, there is a continuing need to provide phosphite products based on pentaerythritol which is effective to maintain color stability and which absorb moisture more slowly to maintain their efficacy for longer periods of time in hygroscopic conditions.

One embodiment of the present invention is to provide a low volatility thermally stable diphosphite-based antioxidant having a high pyrolysis temperature.

Another embodiment of the present invention is to provide a diphosphite-based antioxidant having excellent stability to hydrolysis when exposed to moisture for a certain time.

Yet another embodiment of the present invention is to provide a diphosphite-based antioxidant, which maintains the yellowness index as low as possible and maintains the melt-flow index so that decomposition does not occur under processing conditions.

Another embodiment of the present invention is to provide a polymer resin composition comprising the antioxidant.

Another embodiment of the present invention is to provide a molded article made of the polymer resin composition.

One embodiment of the present invention provides a diphosphite-based antioxidant represented by the following formula (1).

[Formula 1]

 Another embodiment of the present invention provides a polymer resin composition including a diphosphite-based antioxidant and a polymer resin represented by Chemical Formula 1.

Another embodiment of the present invention provides a molded article manufactured using the polymer resin composition.

Antioxidant according to an embodiment of the present invention is excellent in color stability and melt-flow stability in the polymer resin can be usefully used as an antioxidant in a variety of polymer resins.

One embodiment of the present invention provides a diphosphite-based antioxidant represented by the following formula (1).

[Formula 1]

 Compound represented by the formula (1) has the advantages of high heat resistance, low volatility and excellent hydrolytic stability, the compound of formula (1) includes a pentaerythritol diphosphite-based backbone, it is possible to maintain the color stability better In addition, due to the bulk alkylphenol group bonded to the pentaerythritol diphosphite-based backbone, it is possible to further improve the hydrolytic stability.

The diphosphite-based antioxidant represented by Chemical Formula 1 has excellent thermal stability, low volatility, and excellent stability to hydrolysis, and therefore is not hydrolyzed by moisture in the air during storage.

The diphosphite-based antioxidant of Chemical Formula 1 according to one embodiment of the present invention may be prepared by the following process.

Pentaerythritol is reacted with phosphorus trihalide and 2-methyl-4,6-di-tert-butylphenol in the presence of tri-n-alkylamine.

As the phosphorus trihalide, PCl ₃ , PBr ₃ , PI _3, or a combination thereof may be used.

More specifically, the reaction is mixed with pentaerythritol and tri-n-alkylamine. In this case, the tri-n alkylamine is based on 100% by weight of the diphosphite-based antioxidant of Formula 1 as the final product (ie, when 100% by weight is theoretically calculated when calculating the yield of the diphosphite-based antioxidant of Formula 1). On the basis of), amounts in the range of about 0.1% to about 3% by weight can be used. When the amount of the tri-n alkylamine is included in the above range, there may be an advantage that the yield of pentaerythritol diphosphite is maximized.

In addition, the said mixing process can be performed in a solvent. In this case, the amount of the solvent may be used in an amount of about 50% by weight to about 200% by weight based on 100% by weight of the diphosphite-based antioxidant of Formula 1. When the amount of the solvent is included in the above range, there may be an advantage that the yield of pentaerythritol diphosphite is maximized.

The solvent may be selected from the group consisting of xylene, toluene, hexane, heptane, methylene chloride, chloroform, chlorobenzene, ethylbenzene, benzene, and combinations thereof.

After adding phosphorus trihalide to the mixture, the mixture is heated to 70 ° C to 90 ° C over 2 hours to 3 hours, and maintained at the elevated temperature for 2 hours to 3 hours. The product obtained is then cooled to 50 ° C. to 70 ° C. and 2-methyl-4,6-di-tert-butylphenol is added.

The resulting mixture is heated to 130 ° C. to 150 ° C. over 2 hours to 3 hours, and maintained at an elevated temperature for 8 hours to 10 hours. The product obtained is then cooled to 90 ° C. to 110 ° C. and neutralized by addition of solvent and tri-n-alkylamine to the cooled product. At this time, the solvent and the tri-n alkylamine is based on 100% by weight of the diphosphite-based antioxidant of Formula 1 Amounts in the range from about 50% to about 100% by weight from about 0.5% to about 3% by weight can be used. When the amount of the solvent and the tri-n alkylamine is included in the above range, there may be an advantage that the yield of pentaerythritol diphosphite is maximized. The solvent may be selected from the group consisting of xylene, toluene, hexane, heptane, methylene chloride, chloroform, chlorobenzene, ethylbenzene, benzene, and combinations thereof.

The obtained neutralization product is heat-filtered at 100 degreeC-120 degreeC, an amine compound is added, and the normal process of crystallizing and filtering the obtained product is performed. The amine-based compound is used to increase the hydrolytic stability of the product, for example triisopropanolamine, triethylamine, tributylamine, hexamethylenetriamine or a combination thereof may be used. The content of the amine compound may be used in an amount within the range of about 0.1% by weight to about 3% by weight based on 100% by weight of the diphosphite antioxidant of Formula 1. When the amine compound is used in the above range, there may be an advantage that the yield of pentaerythritol diphosphite is maximized.

The tri-n-alkylamine preferably has 3 or more carbon atoms and more preferably less than 10 carbon atoms of the n-alkyl group. Specific examples of the alkyl group include n-propyl, n-butyl, n-pentyl, n-hexyl, and n-butyl and n-pentyl are preferable. Specific examples of the tri-n-alkylamine include tri-n-butyl amine, tri-n-pentyl amine, or a combination thereof. Tri-n-butylamine is most preferred as the tri-n-alkylamine .

In this case, the mixing ratio of pentaerythritol, phosphorus trihalide and 2-methyl-4,6-di-tert-butylphenol may be 1: 2.0 to 2.2: 2.0 to 2.2 moles. When the mixing ratio of pentaerythritol, phosphorus trichloride and 2-methyl-4,6-di-tertiary-butylphenol is included in the above range, side reactions can be reduced and reaction yield can be increased.

The reaction can be carried out under a nitrogen atmosphere as a whole.

Another embodiment of the present invention provides a polymer resin composition including a diphosphite-based antioxidant and a polymer resin represented by Chemical Formula 1.

The content of the diphosphite-based antioxidant may be 0.01 part by weight to 5 parts by weight, and 0.01 part by weight to 1 part by weight based on 100 parts by weight of the total polymer resin. If the content of the diphosphite-based antioxidant is out of the above range, there may be a problem that a phenomenon such as plate-out or blooming occurs.

The polymer resin is selected from the group consisting of polyolefins, polyesters, polycarbonates, polyamides, polyurethanes, polysulfones, polyimides, polyphenylene ethers, polystyrenes, acrylic polymers, polyacetals, halide containing polymers, and combinations thereof. It may be. The acrylic polymer may include polyacrylate, polymethacrylate, polyacrylonitrile, or a combination thereof. The halide-containing polymer may include polyvinyl chloride, polyvinyl bromide, polyethylene chloride, or a combination thereof. Can be. Moreover, polypropylene, polyethylene, or a combination thereof is mentioned as said polyolefin. As the polymer resin, polyolefin may be more suitable.

In addition, the polymer resin composition may further include an additive, and examples thereof include a heat stabilizer. As the heat stabilizer, calcium stearate, zinc stearate, magnesium stearate, barium stearate, or the like may be used.

The amount of the additive may be 0.01 to 0.5 parts by weight based on 100 parts by weight of the polymer resin. If the amount of the additive is out of the above range, there may be a problem that a phenomenon such as plate-out or blooming occurs .

In addition, the polymer resin composition may further include a hindered phenol antioxidant. Representative examples of the hindered phenol antioxidants include tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane (Tetrakis (methylene-3- (3,5) -di-tert-butyl-4-hydroxyphenyl) propionate) methane), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (octadecyl-3- (3,5) -di-tert-butyl-4-hydroxyphenyl) propionate) or a combination thereof. The amount of the hindered phenol antioxidant may be 0.01 part by weight to 1 part by weight based on 100 parts by weight of the polymer resin.

In addition, the polymer resin composition may further include an ultraviolet stabilizer. Examples of such UV stabilizers include poly-{[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethyl-4-piperidyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (Poly- { [6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidyl) imino]}), poly- (N-beta-hydroxyethyl-2,2,6,6-tetramethyl-4 Poly- (N-Beta-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate), bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate (Bis (2,2,6,6-Tetramethyl-4-Piperidinyl) sebacate), etc. The amount of the UV stabilizer used is 0.01% by weight based on 100 parts by weight of the polymer resin. Parts to 1 part by weight.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.

Antioxidant Production

(Example 1)

A reflux cooler, thermometer, and reactor were mounted in a 1000 ml four-way reactor, and a nitrogen atmosphere was prepared. 34.0 g (0.25 mol) of pentaerythritol, 0.5 g (0.005 mol) of triethylamine, and 157.3 g of solvent xylene were added to the reactor.

Subsequently, 72.3 g (0.53 mol) of phosphorus trichloride was added over 2 hours while stirring slowly at room temperature. After the addition was completed, the mixture was aged for 1 hour at room temperature and heated up to 80 ° C. over 2 hours. After aging at 80 ° C. for 2 hours, after cooling to 60 ° C., 115.8 g (0.53 mol) of 2-methyl-4,6-di-tert-butylphenol was added to the reactor.

After the addition was completed, the reactor temperature was raised to 148 ° C. over 2 hours and aged at this temperature for 8 hours. In the aging process, 10.0 g (0.09 mol) of triethylamine was further added to improve reactivity.

When the reaction was completed, the reaction was cooled to 100 ℃, neutralized by adding 107.3g of xylene and 2g of triethylamine to the cooling product. After neutralization, heat filtration was performed at 110 ° C., and 1.13 g of triisopropanolamine was added thereto.

The product obtained was then crystallized with cooling to 10 ° C. and filtered at 10 ° C. The filtrate was washed with 200 g of acetone in which 0.85 g of triisopropanolamine was dissolved, and then dried in a vacuum drying oven to obtain a white solid product. 112.5 g of product was obtained, yield was 71.1%.

The results of measuring the physical properties of the prepared product are as follows. In the following experimental results, 1 H-NMR was measured using Varian Gemini-300 (CDCl ₃ , ppm), IR was measured using a BIORAD spectrometer.

1 H-NMR (CDCl ₃ , δ ppm): 7.27 (s, 2H, aromatic protons), 7.08 (s, 2H, aromatic protons), 4.74 4.59 (m, 4H, methyl group of pentaerythritol), 4.36 4.33 (d, 2H , methyl group of pentaerythritol, 3.64 3.57 (t, 2H, methyl group of pentaerythritol), 2.40 (s, 6H, methyl groupof 4,6-di-tert-buthyl-2-methyl phenol), 1.46 (s, 18H, tert-butyl group of 4,6-di-tert-buthyl-2-methyl phenol), 1.28 (s, 18H, tert-butyl group of 4,6-di-tert-buthyl-2-methyl phenol).

31 P-NMR (CDCl ₃ , δ ppm): 121.8 (Product)

IR data (cm ^-1 ): 3034.3 (w, aromatic CH stretch), 2956.2 2874.9 (s, aliphatic CH stretch), 1477.0 (s, CH ₂ bend), 1361.1 (m, CH ₃ bend), 1020.7 (s, CO stretch), 841.7 (s, PO)

(Comparative Example 1)

Tris (2,4-di-t-butylphenyl) phosphite of the formula (2) was used.

(2)

(Comparative Example 2)

Trisnonylphenyl phosphite of the formula (3) was used.

(3)

(Comparative Example 3)

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite of Formula 4 was used.

[Chemical Formula 4]

(Comparative Example 4)

Tetrakis- (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite of formula 5 was used.

[Chemical Formula 5]

[Analysis]

<Thermo-gravimetric analysis (TGA) experiments>

In order to measure the thermal stability of the compounds of Examples 1 and Comparative Examples 1 to 4 TGA was measured, the results are shown in Table 1 below. The TGA experiment was carried out by heating the compound at a rate of 20 ° C. in an N ₂ atmosphere and measuring the temperature until the weight loss rates reached 5%, 10% and 50% by weight. This experiment was conducted using a TA INSTRUMENTS TGA (TA 2100: TA Instruments) measurement device.

Weight loss rate (%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 5% 276.93 ℃ 265.81 ℃ 292.35 ℃ 273.76 ℃ 345.47 ℃ 10% 292.80 ℃ 302.88 ℃ 312.48 ℃ 295.85 ℃ 365.28 ℃ 50% 345.81 ℃ 382.34 ℃ 371.14 ℃ 405.98 ℃ 410.77 ℃

As shown in Table 1, it can be seen that the compound of Example 1 has to reach a very high temperature, 5%, 10% and 50% weight loss rate compared to Comparative Examples 1 to 4. According to this result, it can be seen that the compound of Example 1 shows good high temperature stability and low volatility compared to the compounds of Comparative Examples 1 to 4.

Hydrolysis Stability

The hydrolysis stability for the compounds of Example 1 and Comparative Examples 1 to 4 was measured. This is because when a phosphite compound is hydrolyzed by reaction with water, a suitable acidic species is produced, so monitoring the phosphite for alcohol or phenol and acid content determines the degree of hydrolysis and, as a result, the suitability of the product for use. It is to see.

Hydrolysis safety was compared by measuring the acid value every 8 hours while the compound was exposed to air for 48 hours at 60 ° C. relative humidity (RH) 100%. The acid value was determined by titrating the exposed sample g with KOH, calculating the KOH content required to the neutralization point as a value (mg KOH / g sample) for the sample 1g, and the acid value results are shown in Table 2 below.

0 hours 8 hours 16 hours 24 hours 32 hours 40 hours 48 hours Comparative Example 3 0.04 0.4 28.65 185.82 247.32 240.94 254.1 Comparative Example 2 0.41 16.36 74.2 110.83 115.95 115.19 115.15 Example 1 0.01 0.10 0.77 219.20 293.20 325.10 331.10

In general, the lower the acid value, the better the hydrolytic stability. Looking at the results shown in Table 2, the hydrolysis proceeds after Example 1 in 24 hours, Comparative Example 2 can be seen that the hydrolysis proceeds actively after 8 hours, Comparative Example 3 after 16 hours . Therefore, it can be seen that the compound of Example 1 is superior in hydrolysis stability as compared with Comparative Examples 2 and 3.

In particular, it can be seen that Example 1 has excellent initial hydrolysis stability since there is almost no initial numerical change. In addition, Example 1 can be seen that the hydrolysis reaction is almost completed only after about 40 to 48 hours.

On the contrary, in Comparative Example 3, the initial hydrolysis stability was somewhat similar, but after about 32 hours, the hydrolysis reaction was almost completed, and Comparative Example 2 also showed that the initial hydrolysis stability was not good.

[Resin composition preparation]

(Example 2)

0.15 parts by weight of the compound prepared in Example 1 and 0.05 parts by weight of calcium carbonate were added to 1 part by weight of a polypropylene homopolymer and mixed, and the mixture obtained was mixed with 99 parts by weight of a polypropylene homopolymer. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

(Comparative Example 5)

Instead of the compound prepared in Example 1, except that the compound of Comparative Example 1 was used in the same manner as in Example 2 to prepare a polymer resin composition.

(Comparative Example 6)

A polymer resin composition was prepared in the same manner as in Example 2, except that the bis (2,4-dicumylphenyl) pentaerythritol diphosphite product of Formula 6 was used instead of the compound prepared in Example 1. Prepared.

[Chemical Formula 6]

(Comparative Example 7)

0.05 weight part of calcium carbonate was added to 1 weight part of polypropylene homopolymers, and it mixed, and the obtained mixture and 99 weight part of polypropylene homopolymers were mixed. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

* Melt Flow Index (MFI) Measurement

The polymer resin composition prepared according to Example 2 and Comparative Examples 5 to 7 was introduced into a twin screw extruder having a die diameter of 37 mm and L / D 40 at a speed of 10 kg per hour.

The extrusion temperature was 190 ° C./195° C./200° C./205° C./210° C./215° C. from the upper end to the rear end. The extrusion temperature was extruded at an axial rotation speed of 150 rpm under 10,000 ccm nitrogen to prepare a compounding pellet.

The prepared compounding pellets were subjected to multiple extrusions from 1 to 5 times using a single screw extruder of L / D 25 in a twin screw extruder. The temperature of the single screw extruder was 230 ° C./250° C./255° C. from the upper end to the rear end, and was extruded at an axial rotation speed of 25 rpm under air.

In addition, using only the polypropylene homopolymer resin, polypropylene homopolymer compounding pellets were prepared according to the compounding pellet process.

The melt index at a load of 2.16 kg at 230 ° C. was measured using a melt index measuring device of the pellets extruded once, the pellets extruded three times, and the compounding pellets among the multi-extruded pellets prepared in the above process. The results are shown in Table 3 below. In Table 2, pass 1 refers to pellets extruded once, and pass 3 refers to pellets extruded three times.

Comparative Example 7 Example 2 Comparative Example 5 Comparative Example 6 Compounding Pellets 4.404 3.345 3.693 3.408 Pass 1 6.730 4.120 7.060 6.160 Pass 3 11.050 5.180 38.080 49.810

Polymers, such as polypropylene, typically tend to break or cause chain breaks by processing at higher temperatures for a period of time. This will result in an increase in the melt index.

In the results shown in Table 3, in the case of compounding pellets, Example 2 and Comparative Examples 5 and 6 all show similar MFI values. However, in the case of pellets extruded once, comparative results 5 and 6 were somewhat higher than those in Example 2. In addition, in the case of pellets extruded three times, Comparative Examples 5 and 6 were significantly higher than those in Example 2, and also very high compared to Comparative Example 7 in which no antioxidant was used. In the case of Example 2, since the MFI value did not increase significantly even after several times of extrusion, it can be predicted that the antioxidant played an appropriate role in the resin composition. As a result, it can be seen that the antioxidant effect is superior to the compounds used in Comparative Examples 5 and 6.

* Yellow Index measurement

The yellow indexes for the pellets extruded once, the pellets extruded three times, the pellets extruded five times and the compounding pellets of the multi-extruded pellets prepared according to Examples 2 and Comparative Examples 5 to 7 were measured by a spectrophotometer ( Hunterlab ultrascan PRO) and the results are shown in Table 4 below. In Table 4, pass 1 refers to pellets extruded once, and pass 3 refers to pellets extruded three times. In addition, the yellow index difference (ΔYI) of the pellet extruded three times and the compounding pellet was calculated and shown in Table 4 below.

Comparative Example 7 Example 2 Comparative Example 5 Comparative Example 6 Compounding Pellets 0.27 -2.23 -2.32 -2.14 Pass 1 1.75 -1.28 -0.91 -1.33 Pass 3 4.18 -0.60 -0.39 -0.29 △ YI 3.91 1.63 1.93 1.85

The lower the YI number, the whiter and less degraded the sample, the higher the YI number, the more yellow and more degraded the sample.

As shown in Table 4, the difference in the yellow index (ΔI) of the pellet of Example 2 is small compared to Comparative Examples 5 to 7 it can be seen that the antioxidant effect is excellent.

(Example 3)

0.10 parts by weight of the compound prepared in Example 1, 0.05 parts by weight of calcium stearate and tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane) 0.05 parts by weight of Tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane) was added to 1 part by weight of polypropylene homopolymer and mixed, and 99 parts of polypropylene homopolymer was added to the obtained mixture. Mixed to the part. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

(Comparative Example 8)

A polymer resin composition was prepared in the same manner as in Example 3, except that the compound of Comparative Example 1 was used instead of the compound prepared in Example 1.

(Comparative Example 9)

Instead of the compound prepared in Example 1, except that the compound of Comparative Example 3 was used in the same manner as in Example 3 to prepare a polymer resin composition.

(Comparative Example 10)

0.05 part by weight of calcium stearate and 0.05 part by weight of tetrakis (methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane), 1 part by weight of this mixture and poly 99 parts by weight of propylene homopolymer was mixed. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

* Melt Flow Index (MFI) Measurement

The resin composition prepared according to Example 3 and Comparative Examples 8 to 10 was introduced into a twin screw extruder having a die diameter of 37 mm and L / D 40 at a speed of 10 kg per hour.

The extrusion temperature was 190 ° C./195° C./200° C./205° C./210° C./215° C. from the upper end to the rear end, and extruded at a rotational speed of 150 rpm under a 10,000 ccm nitrogen state to prepare a compounding pellet.

The prepared compounding pellets were subjected to multiple extrusions from 1 to 5 times using a single screw extruder of L / D 25 in a twin screw extruder. The temperature of the single screw extruder was 230 ° C./250° C./255° C. from the upper end to the rear end, and was extruded at an axial rotation speed of 25 rpm under air.

The melt index at a load of 2.16 kg at 230 ° C. was measured using a melt index measuring device of the pellets extruded once, the pellets extruded three times, and the compounding pellets among the multi-extruded pellets prepared in the above process. The results are shown in Table 5 below. In Table 5 below, pass 1 is a pellet extruded once, pass 3 is 3, and pass 5 denotes pellets extruded five times.

Comparative Example 10 Example 3 Comparative Example 8 Comparative Example 9 Pass 1 6.52 3.14 4.70 3.30 Pass 3 11.24 3.70 7.47 3.95 Pass 5 16.90 4.43 11.85 5.26

In the results shown in Table 5, the pellets extruded once and three or five times, MFI values of Comparative Examples 8 and 9 are somewhat higher than those of Example 3, and MFI values of Comparative Example 10 are very high. In particular, it can be seen that Comparative Example 8 is significantly higher than Example 3. If the extrusion is used several times and the MFI value does not increase significantly, it means that the antioxidant plays an appropriate role in the resin composition. Therefore, in the case of Example 3, the MFI value did not excessively increase even after several extrusions, and thus the compound of Example 1 used appropriately served as an antioxidant in the polymer resin composition, and as a result, oxidation It can be seen that the prevention effect is superior to the compounds used in Comparative Examples 8 and 9.

* Yellow Index measurement

The yellow indexes for the pellets extruded once, the pellets extruded three times, and the pellets extruded five times among the multi-extruded pellets prepared according to Examples 3 and Comparative Examples 8 to 10 were spectrophotometers (Hunterlab ultrascan PRO). Measured using, the results are shown in Table 6 below. In Table 6 below, pass 1 is a pellet extruded once, pass 3 is 3, and pass 5 denotes pellets extruded five times.

Moreover, the yellow index difference ((DELTA) I) of the pellet extruded 5 times and the pellet extruded once was calculated, and is shown in following Table 6.

Comparative Example 10 Example 3 Comparative Example 8 Comparative Example 9 Pass 1 2.37 0.47 3.03 0.57 Pass 3 4.26 2.01 5.79 2.19 Pass 5 6.40 3.17 7.56 4.75 △ YI 4.03 2.7 4.53 4.18

As shown in Table 6, the difference in the yellow index (ΔI) of the pellet of Example 3 is small compared to Comparative Examples 8 to 10 it can be seen that the antioxidant effect is excellent.

(Example 4)

0.12 parts by weight of the compound prepared in Example 1 and 0.05 parts by weight of zinc stearate and octadecyl-3 (3,5-di-tert-4-hydroxyphenyl) propionate) (octadecyl-3- (3, 0.03 parts by weight of 5-di-tert-butyl-4-hydroxyphenyl) propionate) was added to 1 part by weight of polyethylene homopolymer and mixed, and 99 parts by weight of polyethylene homopolymer was mixed with the obtained mixture. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

(Comparative Example 11)

Instead of the compound prepared in Example 1, except that the compound of Comparative Example 1 was used in the same manner as in Example 4 to prepare a polymer resin composition.

(Comparative Example 12)

A polymer resin composition was prepared in the same manner as in Example 4, except that the compound of Comparative Example 3 was used instead of the compound prepared in Example 1.

(Comparative Example 13

Instead of the compound prepared in Example 1, except that the compound of Comparative Example 4 was used in the same manner as in Example 4 to prepare a polymer resin composition.

(Comparative Example 14)

Instead of the compound prepared in Example 1, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butyl of formula 7 A polymer resin composition was prepared in the same manner as in Example 4 except that phenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine was used.

[Formula 7]

(Comparative Example 15)

A resin composition was prepared in the same manner as in Example 4, except that the bis (2,4-dicumylphenyl) pentaerythritol diphosphite product of Chemical Formula 6 was used instead of the compound prepared in Example 1. It was.

[Chemical Formula 6]

(Comparative Example 16)

In the same manner as in Example 4, except that the bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite product of Formula 8 was used instead of the compound prepared in Example 1. It carried out to manufacture a resin composition.

[Formula 8]

(Comparative Example 17)

0.05 parts by weight of zinc stearate was added to 99.95 parts by weight of polyethylene homopolymer and mixed. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a polymer resin composition.

Melt Flow Index (MFI) Measurement

The polymer resin composition prepared according to Example 3 and Comparative Examples 11 to 17 was introduced into a twin screw extruder having a die diameter of 37 mm and L / D 40 at a speed of 10 kg per hour.

The extrusion temperature was 190 ° C./195° C./200° C./205° C./210° C./215° C. from the upper end to the rear end and extruded at an axial rotation speed of 150 rpm under 20,000 ccm nitrogen to prepare compounding pellets.

The prepared compounding pellets were subjected to multiple extrusions from 1 to 5 times using a single screw extruder of L / D 25 in a twin screw extruder. The temperature of the single screw extruder was 230 ° C./250° C./255° C. from the upper end to the rear end and extruded at 25 rpm speed under air.

In addition, using only polyethylene homopolymer resin, polyethylene homopolymer compounding pellets were prepared according to the compounding pellet process.

The melt index at a load of 10 kg at 230 ° C. was measured using a melt index measuring device of the pellets extruded once, the pellets extruded three times, and the compounding pellets among the multi-extruded pellets prepared in the above process. The results are shown in Table 7 below. In Table 7, pass 1 is a pellet extruded once, pass 3 is a pellet three times, Pass 5 is a pellet extruded five times.

Comparative Example 17 Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 4 Comparative Example 14 Comparative Example 15 Comparative Example 16 Pass 1 5.991 7.638 8.145 8.160 8.159 8.038 8.043 8.180 Pass 3 3.784 7.107 8.067 7.676 8.250 7.518 7.794 8.266 Pass 5 2.907 6.391 7.825 6.666 8.261 6.725 7.753 7.915

Polyethylene may increase in molecular weight due to crosslinking and oxidation. When evaluating polyethylene by melt index, and basically for all polymers, it is desirable that the melt index does not change from start to finish.

According to the results shown in Table 7, in the case of Example 4, the MFI value was not excessively increased even after several times of extrusion, and thus the product of Example 4 used appropriately serves as an antioxidant in the resin composition. As a result, it can be seen that the antioxidant effect is superior to the compound used in the comparative example.

* Yellow Index measurement

The yellow index of the pellets extruded once, the pellets extruded three times, and the pellets extruded five times among the multi-extruded pellets prepared according to Examples 4 and Comparative Examples 11 to 17 was measured by a spectrophotometer (Hunterlab ultrascan PRO). Measured using, the results are shown in the table below. In the following table, pass 1 means pellets extruded once, pass 3 means pellets three times, and pass 5 means pellets extruded five times.

Moreover, the yellow index difference ((DELTA) I) of the pellet extruded 5 times and the pellet extruded once was calculated, and is shown in following Table 8.

Comparative Example 17 Comparative Example 11 Comparative Example 12 Comparative Example 13 Example 4 Comparative Example 14 Comparative Example 15 Comparative Example 16 Pass 1 -3.54 -3.23 -3.55 -3.58 -3.59 -3.49 -3.67 -3.45 Pass 3 -3.09 -2.07 -2.84 -2.42 -3.35 -2.33 -3.16 -3.09 Pass 5 -2.78 -1.52 -1.85 -1.76 -2.69 -1.52 -1.95 -1.99 △ YI 0.75 1.71 1.7 1.82 0.9 1.97 1.72 1.46

As shown in Table 8, the difference in the yellow index (ΔI) of the pellet of Example 4 is small compared to Comparative Examples 11 to 17 it can be seen that the antioxidant effect is excellent.

From the above results, it can be seen that the phosphite compositions of Examples 2 to 4 stabilize especially the resin during the high temperature process with little or no relative change in melt index and / or color even after multiple extrusions.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (8)

Diphosphite-type antioxidant represented by following General formula (1).
[Chemical Formula 1]

Diphosphite-type antioxidant represented by following General formula (1); And
Polymer resin
Polymer resin composition comprising a.
[Chemical Formula 1]

3. The method of claim 2,
The content of the diphosphite-based antioxidant is 0.01 to 5 parts by weight based on 100 parts by weight of the polymer resin polymer resin composition. 3. The method of claim 2,
The polymer resin is selected from the group consisting of polyolefins, polyesters, polycarbonates, polyamides, polyurethanes, polysulfones, polyimides, polyphenylene ethers, polystyrenes, acrylic polymers, polyacetals, halide containing polymers, and combinations thereof. Will be a polymer resin composition. 3. The method of claim 2,
The polymer resin is a polyolefin polymer resin composition. 3. The method of claim 2,
The polymer resin composition is a polymer resin composition further comprises an additive. The method according to claim 6,
The content of the additive is a polymer resin composition of 0.01 to 0.5 parts by weight based on 100 parts by weight of the polymer resin. The molded article manufactured using the polymer resin composition of any one of Claims 2-7.