KR20120086582A - Oligomer-type phosphite-based antioxidantexhibiting high heat resistance and polymer resin composition inclduing same - Google Patents

Abstract

PURPOSE: An oligomer type phosphite based antioxidant is provided to have excellent thermal stability, high hydrolysis stability, not to have environment contamination problem, to be easily handled, and to be suitably used as an antioxidant for various polymer resins. CONSTITUTION: An oligomer type phosphite based antioxidant is in chemical formula 1. In chemical formula 1, R^1-R^12 is same or different each other, is hydrogen or an alkyl group, and n is an integer from 1-10. The oligomer type phosphite based antioxidant has weight average molecular weight of 1,000-5,000. A polymer resin composition comprises the oligomer type phosphite antioxidant, and a polymer resin. The content of the phosphite based antioxidant is 0.01-0.5 parts by weight based on 100.0 parts by weight of the polymer resin.

Description

High heat resistant oligomer type phosphite-type antioxidant and the polymer resin composition containing the same TECHNICAL FIELD

It is to provide a high heat resistant oligomeric phosphite-based antioxidant excellent in heat resistance and a polymer resin composition comprising the same.

In general, resin compositions used to prepare plastic products include stabilizers against oxidative processes that may be caused by unwanted changes such as chain breakage, crosslinking, discoloration, as well as changes in the mechanical or physical properties of the resin. in need.

Antioxidants are mainly used as such stabilizers, and representative examples of the antioxidants include antioxidants including a shielded phenolic line or phosphorus. Use of such an antioxidant in the resin composition is the most convenient and effective way to protect the resin from denaturation.

Representative examples of phosphorus-based antioxidants include pentaerythritol diphosphite-based antioxidants, which are used in many applications and are very effective materials for maintaining color stability.

However, such phosphorus antioxidants are poor in resistance to hydrolysis due to the nature of phosphorus. Accordingly, the antioxidant used in the form of powder or granules absorbs moisture when stored, so that the stabilizer is agglomerated or agglomerated, and thus is difficult to handle when supplied and used. In addition, hydrolysis may occur when exposed to moisture, thereby reducing stabilization characteristics, and when such an antioxidant is used in the resin composition, there is a problem of deteriorating its characteristics.

Thus, organic phosphites having aryl groups shielded to have hydrolysis resistance have been used. Materials widely used as organic phosphites with such masked aryl groups include tris- (2,4-di-tert-butylphenyl) phosphite, which possesses good hydrolytic stability. However, due to their low molecular weight, they tend to volatilize during resin processing, are not as effective as desired for color stability and melt-flow stabilization, and have low solubility in resin and plate-out or blooming due to their high melting point. There was a problem that occurred such as (blooming).

In addition, the antioxidant in monomer form can be easily volatilized to emit a bad smell when used in a resin composition requiring a high processing temperature, and may cause problems such as migration, evaporation, and extraction in the resin composition.

One embodiment of the present invention is to provide a high heat resistance oligomeric phosphite-based antioxidant excellent in heat resistance.

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 is to provide an oligomeric phosphite-based antioxidant represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ¹² are the same as or different from each other, and are hydrogen or an alkyl group,

n is an integer from 1 to 10.

The weight average molecular weight (Mw) of the oligomeric phosphite-based antioxidant may be 1,000 to 5,000.

Another embodiment of the present invention provides a polymer resin composition comprising an oligomeric phosphite-based antioxidant and a polymer resin represented by the formula (1).

The polymer resin may be polyolefin, polyethylene, polypropylene, polyester, polycarbonate, polyamide, polyurethane, polysulfone, polyimide, polyphenylene ether, styrene polymer, acrylic polymer, polyacetal, halide containing polymer and their It may be selected from the group consisting of a combination.

The phosphite antioxidant may be present in an amount of 0.01 parts by weight to 0.5 parts by weight based on 100 parts by weight of the polymer resin.

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

Excellent heat resistance according to an embodiment of the present invention, in particular, long-term heat resistance, high hydrolysis stability, there is no problem of environmental pollution, easy to handle, it can be usefully used as an antioxidant in various polymer resins.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Oligomeric phosphite-based antioxidant according to an embodiment of the present invention may be represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ¹² are the same as or different from each other, and are hydrogen or an alkyl group.

R ¹ to R ¹² may be the same as or different from each other, and may be hydrogen, a methyl group, a tertiary butyl group, or a tertiary pentyl group.

n may be an integer from 1 to 10.

In the present specification, unless specifically defined, an alkyl group means a C1 to C4 linear or branched alkyl group.

The weight average molecular weight (Mw) of the oligomeric phosphite-based antioxidant may be 1,000 to 5,000. When the weight average molecular weight of the oligomeric phosphite-based antioxidant is included in the above range, while exhibiting appropriate oligomer properties, the melting point is low, there is an advantage that the compatibility with the polymer resin is more excellent.

The phosphite-based antioxidant represented by the formula (1) is an oligomer type, which is excellent in compatibility and durability with the polymer resin when used in the polymer resin composition as compared to the monomer type antioxidant or the compound type antioxidant. In addition, in general, small molecular weight antioxidants, such as monomeric antioxidants or compound type antioxidants, when used in the resin composition, can easily volatilize and give off a bad odor. Low solubility in water, which may cause problems such as migration to the surface), evaporation, and extraction, whereas an oligomeric antioxidant according to one embodiment of the present invention has a high molecular weight and a high molecular weight. This problem can be reduced because of the closer oligomeric form.

In addition, the oligomer-type phosphite-based antioxidant represented by the formula (1) includes a functional group derived from 4,4'-biphenol having a high melting point and structurally very stable, and can exhibit high heat resistance. Thus, the antioxidant according to one embodiment of the present invention can be usefully used in the production of engineering plastics (engineering plastics) that require a high processing temperature.

In addition, the oligomeric phosphite-based antioxidant represented by Formula 1 includes a functional group derived from 4,4'-biphenol having a high melting point, but the melting point of the oligomeric phosphite-based antioxidant of Formula 1 Silver has a melting point of 20 to 90 ° C., which is lower than 100 ° C., thus reducing problems such as deposition or blooming due to good compatibility with resins and solubility in resins compared to conventional high melting point phosphite-based antioxidants. It can be used for various resins.

In addition, by combining the functional group is three-dimensionally shielded on the sock end, there is an advantage of excellent hydrolytic stability. The oligomeric phosphite-based antioxidant according to an embodiment of the present invention represented by the formula (1) can be prepared by the following two methods. Hereinafter, each manufacturing method will be described in detail.

1) first way

4,4'-biphenol and phosphorus trihalide are reacted in the presence of a catalyst to prepare tetrahalogen 4,4'-biphenyl diphosphite.

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

Tri-n-alkylamine may be used as the catalyst. In this tri-n-alkylamine, the carbon number of the n-alkyl group may be 2 or more and less than 10. Specific examples of such tri-n-alkylamines include tri-n-ethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, di-n-butyl-n-pentylamine Combinations of tertiary alkyl amines can be used.

The mixing ratio of the 4,4'-biphenol and phosphorus trihalide may be 1: 1 to 1: 5 molar ratio. When the mixing ratio of 4,4'-biphenol and phosphorus trihalide is included in the above range, side reaction may be minimized.

The reaction can be carried out in an inert atmosphere such as nitrogen and argon.

In addition, the reaction can be carried out in a solvent. In this case, the solvent may be selected from the group consisting of xylene, toluene, hexane, heptane, methylene chloride, chloroform, chlorobenzene, ethylbenzene, benzene, and combinations thereof.

The reaction product, tetrahalogen 4,4'-biphenyl diphosphite, is then reacted with an alkyl substituted phenol.

The alkyl substituted phenol may be selected from the group consisting of 2,4,6-tri-alkyl phenol, di-alkyl phenol and combinations thereof, and specific examples are 2,4,6-tri-tert-butyl Phenol, 2,4-di-tert-butylphenol, 2,4,6-tri-tert-pentylphenol, 2-3-butyl-4-methylphenol, 2,6-di-tert-butyl Phenol, 2,4-di-tert-pentylphenol, 2-methyl-4,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-methyl- 6-tert-butylphenol, 2,6-dimethylphenol, or a combination thereof. As the alkyl substituted phenol, 2,6-di-tert-butylphenol, 2,4-di-tert-methylphenol, 2-methyl-6-tert-butylphenol, 2-methyl-4,6 Preference is given to using -di-tert-butylphenol, 2,6-dimethylphenol or combinations thereof.

The alkyl substituted phenol may be used in an amount of 1.9 mol to 2.2 mol based on 1 mol of the trihalogenated compound. When the alkyl substituted phenol is used in the content of the above range, there may be an advantage that it is easy to remove the excess phenol and obtain a good quality product.

The reaction process between the reaction product and the alkyl-substituted phenol may be performed at room temperature to about 120 to about 150 ° C, and then at a temperature of about 20 to about 30 hours.

According to this process, an oligomeric phosphite-based antioxidant represented by Chemical Formula 1 may be prepared.

2) second way

Phosphorus trihalide and alkyl substituted phenols are reacted in the presence of a catalyst to produce alkylhalogenphosphites.

The alkylhalogenphosphite is then reacted with 4,4'-biphenol.

In this production method, the phosphorus trihalide, alkylated phenol, mixing ratio, reaction conditions, and the like are the same as those of the second method described above, and thus, detailed description thereof is omitted.

According to the above methods, a phosphite-based oxide represented by Formula 1 according to an embodiment of the present invention can be prepared. In addition, the method is a step by step of the manufacturing process, the first method and the second method can be carried out by selecting appropriately according to the type of alkylphenol used. If the materials used are mixed and reacted in a batch, it is not possible to prepare a phosphite oxide represented by the formula (1) according to an embodiment of the present invention.

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

The polymer resin composition includes the phosphite-based antioxidant and a polymer resin. In this case, the content of the phosphite-based antioxidant may be 0.01 parts by weight to 0.5 parts by weight based on 100 parts by weight of the polymer resin.

The polymer resin is polyolefin, polyethylene, polypropylene, polyester, polycarbonate, polyamide, polyurethane, polysulfone, polyimide, polyphenylene ether, polystyrene, acrylic polymer, polyacetal, halide containing polymer (polyvinyl chloride , Polyvinyl bromide, polyethylene chloride, etc.) and combinations thereof. Polyolefin may be more suitable as the polymer, and polypropylene, polyethylene, etc. may be mentioned as the polyolefin.

In addition, the polymer resin composition may further include an additive, and examples thereof include a heat stabilizer and an antioxidant. The amount of the additive may be 0.01 to 1 part by weight based on 100 parts by weight of the polymer resin .

(Example)

Hereinafter, specific embodiments of the present invention are presented. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

Antioxidant Production

Example 1 Phosphoric acid 4 ′-[bis- (2-tert-butyl-6-methyl-phenoxy)] phosphanyloxy] -biphenyl-4-yl ester bis- (2-3) Phosphorous acid 4 '-[bis- (2-tert-butyl-6-methyl-phenoxy) -phosphanyloxy] -biphenyl-4-yl ester bis- (2-tert- butyl-6-methyl-phenyl) ester)

[Formula 1a]

 (In Formula 1a, n is 2.3, and thus the weight average molecular weight is 1411)

A reflux cooler, thermometer, and reactor were installed in a 1000 ml four-way reactor, and a nitrogen atmosphere was formed. 3.4 g (0.018 mol) and 167.5 g of xylene solvent were added thereto.

The temperature of the reactor was raised to 140 ° C. and aged at this temperature for 20 hours. After aging, the resulting reaction was cooled to 50 ° C., 44.2 g (0.24 mol) of 4,4′-biphenol was added, heated up to 140 ° C., and stirred at this temperature for 20 hours.

After the reaction was completed, the reaction was washed with water and concentrated under reduced pressure. The reaction obtained was cooled to give a white solid product. The yield of the product was 85.6%, yielding 182.8 g. The melting point (Mp) of the product was 62.1 ° C.

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 , ppm): 7.27 7.23 (d, 4H, aromatic protons), 7.19 7.16 (d, 4H, aromatic protons), 7.05 7.02 (d, 4H, aromatic protons), 7.00 6.97 (t, 4H , aromatic protons), 6.52 6.49 (d, 4H, aromatic protons), 2.45 (s, 12H, methyl group of 6-tert-butyl-o-cresol), 1.47 (s, 36H, tert-butyl group protons)

IR data (cm ^-1 ): 3077.0 (w, aromatic CH stretch), 2958.2 2870.2 (s, aliphatic CH stretch), 1601.8 (m, C = C), 1492.1 (s, aromatic C = C), 1415.6 (s, CH ₃ bend), 1203.7 (s, CO), 864.2 (s, PO)

Example 2 Phosphoric Acid 4 '-[bis- (2,4-di-tert-butyl-6-methyl-phenoxy)] phosphanyloxy] -biphenyl-4-yl ester bis- (2,4-di-tert-butyl-6-methyl-phenyl) ester (Phosphorous acid 4 '-[bis- (2,4-di-tert-butyl-6-methyl-phenoxy) -phosphanyloxy] -biphenyl Preparation of -4-yl ester bis- (2,4-di-tert-butyl-6-methyl-phenyl) ester)

[Chemical Formula 1b]

 (In Formula 1b, n is 1.5, and thus the weight average molecular weight is 1349)

A reflux cooler, a thermometer, and a reactor were mounted in a 3000 ml four-necked reactor, and a nitrogen atmosphere was prepared. , 8.1 g (0.044 mol) of tributylamine, and 404.6 g of xylene solvent were added thereto.

The temperature of the reactor was raised to 140 ° C. and aged at this temperature for 20 hours. After aging, the reaction was cooled to 50 ° C., 79.6 g (0.4 mol) of 4,4′-biphenol was added, and again heated to 140 ° C. and stirred at this temperature for 20 hours.

After the reaction was completed, the reaction was washed with water and concentrated under reduced pressure. The reaction obtained was cooled to give a white solid product. The yield of the product was 86.3%, 345.6 g. The melting point (Mp) of the product was 81.8 ° C.

The physical properties of the prepared product were measured in the same manner as in Example 1, as follows.

¹ H-NMR (CDCl ₃ , ppm): 7.27 (s, 4H, aromatic protons), 7.15 7.12 (d, 4H, aromatic protons), 7.05 (s, 4H, aromatic protons), 6.46 6.43 (d, 4H, aromatic protons), 2.44 (s, 12H, methyl group of 4,6-di-tert-buthyl-2-methyl phenol), 1.46 (s, 36H, tert-butyl group protons), 1.31 (s, 36H, tert-butyl group protons)

IR data (cm ^-1 ): 3034.2 (w, aromatic CH stretch), 2960.7-2868.6 (s, aliphatic CH stretch), 1601.6 (m, C = C), 1492.5 (s, aromatic C = C), 1362.1 (m , CH ₃ bend), 1198.4 (s, CO), 850.4 (s, PO)

Example 3 Phosphoric Acid 4 ′-[bis- (2,6-dimethyl-phenoxy)] phosphanyloxy] -biphenyl-4-yl ester bis- (2,6-methyl-phenyl) Preparation of ester (Phosphorous acid 4 '-[bis- (2,6-dimethyl-phenoxy) -phosphanyloxy] -biphenyl-4-yl ester bis- (2,6-dimethyl-phenyl) ester)

[Chemical Formula 1c]

 (In Formula 1c, n is 7.2, and thus the weight average molecular weight is 2831)

A reflux cooler, a thermometer, and a reactor were mounted in a 3000 ml four-stage reactor, and a nitrogen atmosphere was prepared. mol) was added.

After the mixture was aged at room temperature for 5 hours, 300 g of xylene solvent was added and further aged for 15 hours.

After aging, 359.3 g (2.9 mol) of 2,6-dimethylphenol (2,6-xylenol) was added to the product, and the mixture was heated to 120 ° C and aged at this temperature for 20 hours.

When the reaction was completed, the reaction was concentrated under reduced pressure. The reaction obtained was cooled to give a clear white liquid product. Yield of the product was 477.0 g at 87.0%.

The physical properties of the prepared product were measured in the same manner as in Example 1, as follows.

¹ H-NMR (CDCl ₃ , ppm): 7.45 7.30 (m, 4H, aromatic protons), 7.17 7.13 (m, 4H, aromatic protons), 7.02 6.96 (m, 8H, aromatic protons), 6.94 6.87 (m, 4H , aromatic protons), 2.32 (s, 24H, methyl group of 2,6-xylenol)

IR data (cm ^-1 ): 3035.8 (w, aromatic CH stretch), 2955.1 2855.3 (w, aliphatic CH stretch), 1601.5 (w, C = C), 1491.1 (s, aromatic C = C), 1164.9 (s, C = O), 865.2 (s, PO)

Example 4 Phosphoric acid 4 '-[bis- (2,4-di-tert-butyl-phenoxy)] phosphanyloxy] -biphenyl-4-yl ester bis- (2,4) Phosphorous acid 4 ′-[bis- (2,4-di-tert-butyl-phenoxy) -phosphanyloxy] -biphenyl-4-yl ester bis- (2,4- di-tert-butyl-phenyl) ester)

≪ RTI ID = 0.0 &

(In Chemical Formula 1d, n is 3.7, and thus the weight average molecular weight is 2221).

In a 3000 ml four-necked reactor, reflux cooler, thermometer, and reactor were used to make CC29, and nitrogen atmosphere was added. 0.028 mol) was added.

After the mixture was aged at room temperature for 5 hours, 300 g of xylene solvent was added and further aged for 15 hours.

After the aging was completed, 618.9 g (3.0 mol) of 2,4-di-tert-butylphenol was added to the product, the temperature was raised to 120 ° C, and aged at this temperature for 20 hours.

When the reaction was completed, the reaction was concentrated under reduced pressure. The reaction obtained was cooled to give a white solid product. The yield of the product was 96.7%, 774.1g was obtained. The melting point (Mp) of the product was 67.2 ° C.

The physical properties of the prepared product were measured in the same manner as in Example 1, as follows.

1 H-NMR (CDCl ₃ , ppm): 7.50 7.43 (m, 4H, aromatic protons), 7.40 7.32 (m, 4H, aromatic protons), 7.31 7.29 (m, 4H, aromatic protons), 7.27 7.18 (m, 4H, aromatic protons), 7.15 7.06 (m, 4H, aromatic protons), 1.38 (s, 36H, tert-butyl group protons), 1.30 (s, 36H, tert-butyl group protons)

IR data (cm ^-1 ): 3034.8 (w, aromatic CH stretch), 2960.5 2867.8 (s, aliphatic CH stretch), 1602.5 (m, C = C), 1491.1 (s, aromatic C = C), 1361.8 (m, CH ₃ bend), 1192.4 (s, CO), 855.0 (s, PO)

(Comparative Example 1)

Tris- (2,4-di-tert-butylphenyl) phosphite of Formula 2 was used. Melting point (Mp) of this compound was about 181-187 degreeC.

[Formula 2]

(Comparative Example 2)

Tetrakis (2,4-di-tert-butylphenyl) -1,1-biphenyl-4,4'-diylbisphosphonite (Tetrakis (2,4-di-tert-butylphenyl)) -1,1-biphenyl-4,4'-diylbisphosphonite) was used. The melting point (Mp) of this compound was about 93 to 99 ° C.

(3)

[Analysis]

<Thermo-gravimetric analysis (TGA) experiments>

In order to determine the thermal stability of the products prepared in Examples 1 to 4 and the compounds of Comparative Examples 1 to 3, TGA was measured and the results are shown in Table 1 below. The experimental results shown in Table 1 below are shown by measuring the temperature until the compound loses 10% by weight and 50% by weight by heating the compound at a rate of 20 ° C./min in an N ₂ atmosphere. This experiment was conducted using a TA INSTRUMENTS TGA (TA 2100: TA Instruments) measurement device.

Weight loss rate (%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 10% 380.75 ℃ 345.05 ℃ 283.20 ℃ 325.16 ℃ 299.17 ℃ 319.54 ℃ 50% 420.03 ℃ 410.88 ℃ 411.40 ℃ 440.28 ℃ 339.15 ℃ 409.15 ℃

As shown in Table 1, the products prepared according to Examples 1 to 4 can be seen that the weight loss rate reaches 50% only to reach a very high temperature compared to the compounds of Comparative Examples 1 and 2. As a result, it can be seen that the products prepared according to Examples 1 to 4 have excellent heat resistance.

In addition, it can be seen that the melting points of the products prepared according to Examples 1 to 4 are all 90 ° C. or less, and are excellent in compatibility with the resins as compared to Comparative Examples 1 and 2 having a high melting point of about 93 to 190 ° C. In addition, the products prepared according to Examples 1 to 4 have a low melting point and an oligomer-like molecular structure, so that better compatibility with resins can be expected compared to Comparative Examples 1 and 2 having a single molecule and a higher melting point. Can be.

[Resin composition preparation]

(Example 5)

0.15 parts by weight of the product prepared in Example 1 and 0.05 parts by weight of songstab SC-100 (thermal stabilizer) were added to 1 part by weight of a polypropylene homopolymer and mixed, and 99 parts by weight of the polypropylene homopolymer was mixed with the obtained mixture . The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a resin composition.

(Example 6)

Instead of the product prepared in Example 1, except that the product prepared in Example 2 was used in the same manner as in Example 5 to prepare a resin composition.

(Example 7)

Instead of the product prepared in Example 1, except that the product prepared in Example 3 was used in the same manner as in Example 5 to prepare a resin composition.

(Example 8)

Instead of the product prepared in Example 1, except that the product prepared in Example 4 was used in the same manner as in Example 5 to prepare a resin composition.

(Comparative Example 3)

In place of the product prepared in Example 1, except that the compound of Comparative Example 1 was used in the same manner as in Example 5 to prepare a resin composition.

(Comparative Example 4)

A resin composition was prepared in the same manner as in Example 5, except that the compound of Comparative Example 2 was used instead of the product prepared in Example 1.

* Melt Flow Index (MFI) Measurement

The resin compositions prepared according to Examples 5 to 8 and Comparative Examples 3 to 4 were charged to 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 extruded at 25 rpm speed 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 2 below. In Table 2, pass 1 refers to pellets extruded once, and pass 3 refers to pellets extruded three times.

(Unit: g / 10 minutes) Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Compounding Pellets 3.46 3.73 3.27 3.60 3.94 3.40 Pass 1 5.54 6.19 5.11 5.40 8.13 5.17 Pass 3 22.10 35.15 14.01 26.84 X 40.65

In the results shown in Table 2, in the case of compounding pellets, Examples 5 to 8 and Comparative Examples 3 and 4 all show similar MFI values. However, in the case of pellets extruded once, Comparative Example 3 shows similar values as in Examples 5 to 8, while in Comparative Example 4, it is somewhat higher than Examples 5 to 8. In addition, in the case of pellets extruded three times, Comparative Example 3 showed that the MFI value was too high so that the third extrusion did not proceed at all, and Comparative Example 4 showed an excessively high MFI value compared to Examples 5 to 8. Can be. 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. Thus, in Examples 5 to 8, the MFI value did not increase excessively even after several extrusions, and thus the products of Examples 1 to 4 used appropriately as antioxidants in the resin composition, As a result, it can be seen that the antioxidant effect is superior to the compounds of Comparative Examples 1 and 2 used in Comparative Examples 3 and 4.

(Example 9)

0.10 parts of the product prepared in Example 1, 0.05 parts of songstab SC-100 (thermal stabilizer) and 0.05 parts of songnox 1010 (antioxidant) were added to 1 part of a polypropylene homopolymer and mixed, and 99 parts of a polypropylene homopolymer was added to the obtained mixture. Mixed in. The obtained final mixture was mixed for 30 minutes using a tubla blender to prepare a resin composition.

(Example 10)

A resin composition was prepared in the same manner as in Example 9, except that the product prepared in Example 2 was used instead of the product prepared in Example 1.

(Example 11)

A resin composition was prepared in the same manner as in Example 9, except that the product prepared in Example 3 was used instead of the product prepared in Example 1.

(Example 12)

A resin composition was prepared in the same manner as in Example 9, except that the product prepared in Example 4 was used instead of the product prepared in Example 1.

(Comparative Example 5)

A resin composition was prepared in the same manner as in Example 9, except that the compound of Comparative Example 1 was used instead of the product prepared in Example 1.

(Comparative Example 6)

A resin composition was prepared in the same manner as in Example 9, except that the compound of Comparative Example 2 was used instead of the product prepared in Example 1.

* Melt Flow Index (MFI) Measurement

The resin compositions prepared according to Examples 9 to 12 and Comparative Examples 5 to 6 were charged to 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.

Compounding pellets prepared in a twin screw extruder were subjected to multiple extrusions from 1 to 5 times using a single screw extruder with L / D 25. 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.

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 the polypropylene homopolymer resin, polypropylene homopolymer compounding pellets were prepared according to the compounding pellet process.

The pellets extruded once, the pellets extruded three times, the pellets extruded five times, and the polypropylene homopolymer compounding pellets prepared by the above process were melted at a load of 2.16 kg at 230 ° C. using a melt index measuring equipment. The melt index of was measured. The results are shown in Table 3 below. In Table 3 below, pass 1 is a pellet extruded once, pass 3 is a pellet extruded three times, and pass5 refers to a pellet extruded five times.

(Unit: g / 10 minutes) Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Comparative Example 8 Pass 1 4.220 4.870 3.600 4.410 5.540 5.070 Pass 3 6.270 7.800 4.720 7.020 9.560 9.780 Pass 5 8.890 11.860 5.930 12.680 15.660 19.240

In the results shown in Table 3, in the case of pellets extruded once, the MFI values of Comparative Examples 7 and 8 are somewhat higher than those of Examples 9 to 12. In addition, when comparing the MFI value of the pellet extruded three times and the MFI value of the pellet extruded once, Comparative Examples 7 and 8 significantly increased compared to Examples 9 to 12, this difference is It can be seen that it is larger than the case.

From these results, in the case of Examples 9 to 12, the MFI value did not increase excessively even after several extrusions, so the products of Examples 1 to 4 used appropriately served as antioxidants in the resin composition. As a result, it can be seen that the antioxidant effect is superior to the compounds of Comparative Examples 1 and 2, used in Comparative Examples 7 and 8.

* 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 among the multi-extruded pellets prepared according to Examples 5 to 8 and Comparative Examples 3 to 4 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.

(No unit) Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Compounding Pellets -1.520 -1.820 -3.640 -2.100 -2.430 -2.120 Pass 1 1.02 0.83 -1.10 0.39 -0.43 0.65 Pass 3 1.94 1.42 0.31 1.33 X 2.01 △ YI 3.46 3.24 3.95 3.43 X 4.13

As shown in Table 4, since the yellow index difference (ΔYI) of the pellets of Examples 5 to 8 is smaller than that of Comparative Example 4, it can be seen that the antioxidant effect is excellent. In addition, in the case of Comparative Example 3, the change in the yellow index during one extrusion is small, but it is impossible to apply practically because three times extrusion can not be performed.

* Long Term Thermal Stability (LTTS) measurement

1) 135 ℃ measurement

The resin compositions prepared according to Examples 5 to 8 and Comparative Examples 3 to 4 were charged to 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.

Compounding pellets were injected into the injection molding machine to prepare specimens of size X length X width X thickness 127 X 12.7 X 1.6 mm at a temperature of 220 ° C./230° C./240° C./245° C. from the upper end to the rear end. The starting point showing brittleness was recorded while the prepared specimen was thermally deteriorated in a gear type oven preheated to 135 ° C. The results are shown in Table 5 below.

Comparative Example 3 Comparative Example 4 Example 5 Example 6 Example 7 Example 8 time 16.5 16.5 56.5 26.5 56.5 32.5

As shown in Table 5, since the starting time point showing the brittleness of the compounding pellet using the resin composition of Examples 5 to 8 is very long compared to Comparative Examples 3 and 4, it can be seen that the heat resistance is very excellent.

2) 150 ℃ measurement

Injecting the compounding pellet prepared according to the above process into the injection molding machine to measure the size X length X width X thickness 127 X 12.7 X 1.6mm at 220 ℃ / 230 ℃ / 240 ℃ / 245 ℃ temperature conditions from the upper end to the rear end Prepared. The starting point showing brittleness was recorded while the prepared specimen was thermally deteriorated in a gear type oven preheated to 150 ° C. The results are shown in Table 6 below.

Comparative Example 4 Comparative Example 3 Example 5 Example 6 Example 7 Example 8 time 3.5 1.5 5.5 3.5 9.3 5.5

As shown in Table 6, since the starting time point showing the brittleness of the compounding pellets using the resin compositions of Examples 5 to 8 is very long compared to Comparative Examples 3 and 4, it can be seen that the heat resistance is very excellent.

3) 150 ℃ measurement

The resin compositions prepared according to Examples 9 to 12 and Comparative Examples 5 to 6 were charged to 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.

Compounding pellets were injected into the injection molding machine to prepare specimens of size X length X width X thickness 127 X 12.7 X 1.6 mm at a temperature of 220 ° C./230° C./240° C./245° C. from the upper end to the rear end. The starting point showing brittleness was recorded while the prepared specimen was thermally deteriorated in a gear type oven preheated to 150 ° C. The results are shown in Table 7 below.

Comparative Example 6 Comparative Example 5 Example 9 Example 10 Example 11 Example 12 Unit (days) 16 16 24 21 28 23

As shown in Table 7, since the starting time point showing the brittleness of the compounding pellets using the resin compositions of Examples 9 to 12 is very long compared to Comparative Examples 5 and 6, it can be seen that the heat resistance is very excellent.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (8)

Oligomeric phosphite-based antioxidant represented by the following formula (1).
[Formula 1]

(In Formula 1,
R ¹ to R ¹² are the same as or different from each other, and are hydrogen or an alkyl group,
n is an integer from 1 to 10.) The method of claim 1,
Oligomeric phosphite-based antioxidant having 1 to 4 carbon atoms of the alkyl group. The method of claim 1,
The R ¹ to R ¹² are the same as or different from each other, and are an oligomeric phosphite-based antioxidant which is hydrogen, a methyl group, a tertiary butyl group or a tertiary pentyl group. The method of claim 1,
The oligomeric phosphite antioxidant is an oligomeric phosphite-based antioxidant having a weight average molecular weight of 1,000 to 5,000. An oligomeric phosphite-based antioxidant represented by Formula 1 below; And
Polymer resin
Polymer resin composition comprising a.
[Formula 1]

(In Formula 1,
R ¹ to R ¹² are the same as or different from each other, and are hydrogen or an alkyl group,
n is an integer from 1 to 10.) The method of claim 5,
The polymer resin may be polyolefin, polyethylene, polypropylene, polyester, polycarbonate, polyamide, polyurethane, polysulfone, polyimide, polyphenylene ether, styrene polymer, acrylic polymer, polyacetal, halide-containing polymer and their Polymer resin composition is selected from the group consisting of a combination. The method of claim 5,
The content of the phosphite-based antioxidant 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 polymeric resin composition of any one of Claims 5-7.