KR20140125238A - Storage tank for biodiesel - Google Patents

Abstract

The present invention relates to a polyethylene storage tank for biodiesel, which comprises: a polyethylene resin; a stabilizer including two or more kinds of steric hindrance aminocompounds; an antioxidant, and has below 3% a change rate in tensile strength according to ASTM D 683 specifications between before and after precipitation in biodiesel (B30) at 70 degrees for 500 hours. The polyethylene storage tank can be appropriate for the storage and transportation of fuel including biodiesel by having excellent mechanical properties such as high flexural strength and impact strength and securing high durability to biodiesel.

Description

[0001] STORAGE TANK FOR BIODIESEL [0002]

The present invention relates to a polyethylene storage container for biodiesel, and more particularly, to a biodiesel storage container having high mechanical strength, such as high bending strength and impact strength, while ensuring high durability against biodiesel, ≪ / RTI >

Environmental pollution and depletion of resources, it has the effect of recycling waste resources and reducing CO ₂ , which is a greenhouse gas, and the emission of air pollutants is small, so that interest and use of environmentally friendly biodiesel are gradually increasing. In addition, as the use of biodiesel increases, the durability of containers or pipes made of polyethylene for storing and transporting them is also becoming increasingly important.

Biodiesel is a fuel based on vegetable oil methyl ester (VME), a major representative oilseed rape methyl ester (RME), and RME is known to be aggressive to a plethora of plastics used in automotive fuel systems. In particular, biodiesel can generate a large amount of hydroperoxides due to its instability, thereby promoting the decomposition of polyethylene. Therefore, when the polyethylene storage container stores biodiesel, corrosion or decomposition of the container due to hydroperoxide has made it difficult to store the fuel stably over a period of time over a long period of time.

In order to overcome the long term durability problem, a method of coating the inside of the storage container has been proposed. However, the internal coating is somewhat complicated to carry out in a process, requires a considerable additional production cost, and has a poor economical efficiency.

Further, as another method for overcoming the above problem, a method of using a sterically hindered amine as a stabilizer is proposed in WO 1999-032549 and Korean Patent Laid-open Publication No. 10-2011-0040830. However, the polyethylene resin disclosed in the above prior arts is only excellent in some physical properties, and has insufficient durability against biodiesel and physical properties such as tensile strength, bending strength, impact strength, intrinsic viscosity and the like after long-time precipitation in biodiesel .

Therefore, it is possible to process various types of storage containers with excellent moldability and processability based on excellent mechanical properties such as high flexural strength and tensile strength, and even if the biodiesel is stored for a long period of time, It is necessary to develop a polyethylene storage container for biodiesel which has excellent durability against biodiesel.

WO No. WO999-032549 Korean Patent Publication No. 10-2011-0040830

The present invention is to provide a polyethylene storage container suitable for storage and transportation of fuel including biodiesel by securing high durability against biodiesel while having excellent mechanical properties such as high bending strength and impact strength.

The present invention relates to a polyethylene resin; A stabilizer comprising a first hindered amine compound and a second hindered amine compound comprising a repeating unit represented by Formula 1 below; And an antioxidant, wherein a rate of change in tensile strength according to ASTM D 683 before and after 500 hours of precipitation in biodiesel (B30) at 70 占 폚 is 3% or less.

Hereinafter, a polyethylene storage container for biodiesel according to a specific embodiment of the present invention will be described in detail.

As used herein, the term "biodiesel" is meant to include both liquid and solid fuels containing biodiesel, and is meant to encompass the entire biofuel made from plant itself, vegetable oil ester, or vegetable oil.

Biodiesel B30 herein means a mixture of rapeseed oil methyl ester (RME): diesel in a molar ratio of 30: 70.

In the present specification, the first and second expressions are used to distinguish a hindered amine compound containing a repeating unit represented by the formula (1) from other hindered amine compounds other than the hindered amine compound, And the second term, and the stabilizer may further comprise additional hindered amine compounds in addition to the first and second hindered amine compounds.

In the present specification, the term " hindered amine compound " means a compound in which a bulky atomic group is bonded to nitrogen of an amine and does not have normal reactivity, and a compound having two or more hindered amines means that a bulky atomic group is a nitrogen ≪ / RTI >

According to one embodiment of the invention, a polyethylene resin; A stabilizer comprising a first hindered amine compound and a second hindered amine compound comprising a repeating unit represented by Formula 1 below; And a rate of change in tensile strength according to ASTM D 683 before and after being settled in biodiesel (B30) for 500 hours at 70 DEG C of 3% or less can be provided for the polyethylene storage container for biodiesel.

[Chemical Formula 1]

The present inventors have found that a polyethylene storage container for storing biodiesel can be decomposed by hydroperoxides generated due to the instability of biodiesel and can be stably stored in a polyethylene container capable of storing and transporting a liquid fuel containing biodiesel And confirmed that the polyethylene storage container for biodiesel prepared by applying a specific stabilizer containing two or more sterically hindered amine compounds has excellent durability against hydroperoxides and confirmed the invention and completed the invention.

In particular, the polyethylene storage container for biodiesel has excellent durability against hydroperoxides and has excellent mechanical properties such as high tensile strength, bending strength and impact strength, and is excellent in resin formability or processability, have.

The polyethylene storage container for biodiesel according to one embodiment may exhibit a rate of change of tensile strength of 3% or less at a yield point according to ASTM D 683 before and after 500 hours of precipitation in biodiesel (B30) at 70 ° C. The tensile strength means the force at the highest point of the material, and the rate of change of the tensile strength means the rate of change of the force received by the material at the highest point. The polyethylene storage container for biodiesel exhibits a very high tensile strength even after being dipped in biodiesel for at least 500 hours due to improved durability against hydroperoxide, and the rate of change of tensile strength before and after precipitation may be very small.

The improved durability of the hydroperoxide of the polyethylene storage container for biodiesel can be achieved by applying a specific stabilizing agent comprising a first hindered amine compound and a second hindered amine compound comprising the recurring units of Formula 1 have. More specifically, the first hindered amine compound prevents degradation by hydroperoxides in the interior of the storage container, and the second hindered amine compound prevents decomposition by hydroperoxides outside the storage container, Can stably carry out the storage and transportation of liquid fuel including biodiesel producing hydroperoxides.

The first hindered amine compound having a repeating unit represented by the formula (1) may have a weight average molecular weight of 1,500 g / mol or more, and preferably 1,500 to 10,000 g / mol. The first hindered amine compound is an ultra-high molecular weight amine compound. The first hindered amine compound is an ultra-high molecular weight amine compound, which can not be discharged to the outside due to steric hindrance of an ultrahigh molecular weight compound, It can act as a propellant. That is, the first sterically hindered amine compound eliminates radicals generated by instability of biodiesel, thereby inhibiting hydroperoxide formation and preventing decomposition by hydroperoxides in the molding.

The second hindered amine compound may be a steric hindered amine compound other than the first hindered amine compound, and may have a weight average molecular weight of 500 g / mol or less. The second sterically hindered amine compound is a low molecular weight amine compound which can be discharged to the surface of a storage container due to a repulsive force generated between polar and nonpolar materials and serves as a free radical scavenger for eliminating radicals by providing hydrogen atoms to the radicals can do. That is, the second sterically hindered amine compound can prevent the hydroperoxide decomposition in the molding by suppressing the generation of hydroperoxide by eliminating the radicals generated due to the instability of biodiesel outside the container.

Particularly, the first and second hindered amine compounds are compounds having a steric hindrance by bonding a bulky atom group to an amine nitrogen, and have a cyclic olefin structure. The resonance structure exhibits a reaction characteristic of capturing a radical, Can be erased. Accordingly, the hindered amine compound can suppress the formation of hydroperoxides which cause the decomposition reaction of the polyethylene storage vessel, thereby minimizing the decomposition by hydroperoxides.

That is, the polyethylene storage container may include both the first and second hindered amine compounds to improve the durability against hydroperoxides both inside and outside the storage container, so that the fuel containing biodiesel that produces hydroperoxides Lt; / RTI > The first hindered amine compound and the second hindered amine compound are preferably added in a molar ratio of 2: 1 to 1: 2.

The stabilizer may include 200 to 5000 ppm based on the total weight of the polyethylene storage container for biodiesel. If the content of the stabilizer is too low, the storage container is not excellent in resistance to hydroperoxides, and may be corroded or decomposed from a fuel containing biodiesel.

The hindered amine compound contained in addition to the second hindered amine compound or the first and second hindered amine compounds may be a compound having two or more hindered amines, and specific examples of the hindered amine compound include bis- ( 2,2,6,6-tetramethyl-4-piperidinyl) -s sebacate, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidin- -Ol, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-yl acetate, 2,2,6,6-tetramethyl Piperidin-4-yl 2-ethylhexanoate, 2,2,6,6-tetramethylpiperidin-4-yl stearate, 2,2,6,6-tetramethylpiperidin- Tetramethylpiperidin-4-yl 4-tert-butylbenzoate, bis (2,2,6,6-tetramethylpiperidin-4-yl) Tetramethylpiperidin-4-yl) adipate, bis (2,2,6,6-tetramethylpiperidin-4-yl) Bis (2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis (2,2,6,6-tetramethylpiperidin- Tetramethylpiperidin-4-yl) terephthalate, bis (2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'- Bis (2,2,6,6-tetramethylpiperidin-4-yl) adipinamide, N- (2,2,6,6-tetramethylpiperidin-4- yl) caprolactam, N- (2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris- [N-butyl-N- (2,2,6,6-tetra Methylpiperidin-4-yl)] - s-triazine, 4,4'-ethylene bis (2,2,6,6-tetramethylpiperazin- -Tetramethyl-1-oxylpiperidin-4-yl) phosphite, and their N-hydroxy derivatives or N-oxyl derivatives.

Particularly, the bis- (2,2,6,6-tetramethyl-4-piperidinyl) -sevacate has a molecular weight of 500 g / mol or less and is easily discharged to the outside of the polyethylene storage container. It is more preferable that the bis- (2,2,6,6-tetramethyl-4-piperidinyl) -sebaccate is used as the second hindered amine compound.

The antioxidant may be a phenolic antioxidant; And a phosphorus antioxidant. The phenolic antioxidant has the role of stopping the chain reaction by capturing a peroxy radical in a polyethylene storage vessel and stabilizing it with ROOH, and the phosphorus antioxidant converts ROOH into ROH in a polyethylene storage container to stop the chain reaction The polyethylene storage container can be stabilized by including the two types of antioxidants, so that the degradation by the substances stored in the polyethylene storage container can be minimized. And the antioxidant may include 600 to 5000 ppm based on the total weight of the polyethylene storage container for biodiesel.

In particular, the antioxidant may include the phenolic antioxidant and the antistain agent in a molar ratio of 2: 1 to 1: 2. By mixing the two kinds of antioxidants, it is possible not only to capture pre-existing radicals but also to stabilize the substances that can be radicalized, thereby improving not only thermal stability but also durability against hydroperoxides. In order to maximize the effect of using the two types of antioxidants, the phenol-based antioxidant and the phosphorus-based antioxidant are preferably contained in a molar ratio of 2: 1 to 1: 2.

Examples of the phenolic antioxidant include 3 - {[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyl] oxy} -2,2- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyl] oxy} Hydroxy] -2, < RTI ID = 0.0 > Propanediyl ester, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyoctadecyl ester, 4- [[4,6-bis (octylthio) -1,3,5-tri Azin-2-yl] amino] -2,6-bis (1,1-dimethylethyl) phenol or N, N'-hexamethylenebis (3,5-di- tert.butyl-4-hydroxyhydroxy South Meade) can be used.

Examples of the phosphorus antioxidant include tris (2,4-ditert-butylphenyl) phosphate, 2,4-bis (1,1-dimethylethyl) phenol phosphite or phosphorous [1,1'- , 4'-diylbis-, -tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester.

Particularly, when the phenolic antioxidant is 3 - {[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyl] oxy} -2,2-bis ({[3- butyl-4-hydroxyphenyl) propanoyl] oxy} methyl) propyl 3- (3,5-di-tert- butylphenyl) phosphate, the mixture of the antioxidants has a melting point similar to the temperature at which the polyethylene storage container is molded and processed, thereby exhibiting an effect of preventing oxidation due to dispersion and processing heat.

Meanwhile, the polyethylene storage container for biodiesel according to one embodiment of the present invention may have a rate of change of intrinsic viscosity before and after filling the biodiesel (B30) at 80 ° C for 2500 hours or less, more preferably 40% or less, May be less than or equal to 37%. The intrinsic viscosity indicates the molecular weight of the storage container. The polyethylene storage container having a small change in intrinsic viscosity can maintain the initial mechanical properties even after filling the biodiesel for a long time, Or transported.

Also, the polyethylene storage container for biodiesel may have a rate of change of elongation percentage before and after filling of biodiesel (B30) for 30 hours at 70 ° C of 22% or less, and a rate of change of flexural modulus of 55% or less.

The polyethylene resin may be a homopolymer of ethylene or a copolymer of ethylene and an? -Olefin, and the? -Olefin may be a copolymer of 1-propene, 1-butene, 1-pentene, And 1-decene. In the preparation of the polyethylene storage container for biodiesel, durability and other mechanical properties to the hydroperoxide of the polyethylene storage container to be produced can be appropriately controlled by selecting a suitable? -Olefin.

In particular, when ethylene or an alpha -olefin is mixed with the monomer to form a copolymer, it is preferable that the copolymer contains 0.1 to 10% by weight of -olefins relative to the total weight of the monomers, and 2 to 7% More preferable. If the? -olefin contains less than 0.1% by weight of? -olefin as a density controlling agent, a product having an excessively high density may be produced and the impact strength may be too low. If the? -olefin is contained in an amount exceeding 10% by weight, And the bending strength may be too low.

The storage container for biodiesel includes all components such as plastic parts, tanks, pipes, and supply lines that are exposed to fuel for a long period of time. The storage container may also comprise a multilayer material made according to a co-extrusion technique, which may comprise one or more polyethylene resin layers comprising the ethylene homopolymer or copolymer.

Meanwhile, the polyethylene storage container for biodiesel can be produced by a conventional method for producing a polyethylene resin molded article, comprising the steps of: synthesizing monomers in the presence of a polymerization catalyst; and molding a storage container with a polyethylene resin.

As the polymerization catalyst, a titanium-based Ziegler-Natta catalyst, a chromium-based Philips catalyst, or a zirconium-based metallocene catalyst may be used without limitation.

Then, ethylene can be reacted singly with the monomer, or ethylene and other? -Olefins can be mixed and reacted. The above-mentioned olefins having 3 to 10 carbon atoms can be used as the? -Olefins, and the durability and other mechanical properties to the hydroperoxides of the polyethylene storage containers to be produced can be improved by selecting appropriate proportions of the? -Olefins and ethylene Can be adjusted appropriately.

The synthesis reaction may be carried out in a gaseous, liquid, or solution phase. When the synthesis reaction is carried out in a liquid phase, a hydrocarbon solvent may be used, and the olefin itself may be used as a solvent. The synthesis temperature may be from 0 to 200 캜, preferably from 30 to 150 캜. If the synthesis temperature is less than 0 ° C, the activity of the catalyst is poor. If the synthesis temperature exceeds 200 ° C, the stereoregularity of the polyethylene resin may be deteriorated. The synthesis pressure can be from 1 to 100 atm and preferably from 2 to 40 atm. When the synthesis pressure exceeds 100 atm, it is not preferable from the industrial and economical viewpoints. The synthesis reaction can be carried out by any of batch, semi-continuous and continuous processes.

In addition, heat stabilizers, light stabilizers, flame retardants, carbon black, pigments, antioxidants and the like which are conventionally added can be further added to the polyethylene storage container for biodiesel.

In addition, the step of molding the storage container with the polyethylene resin prepared by synthesizing the monomers in the presence of the polymerization catalyst may be used without limitations, which are known to be used in the production of a molded article of a conventional polyolefin resin.

According to the present invention, it is possible to provide a polyethylene storage container suitable for storing and transporting fuel including biodiesel by securing high durability against biodiesel while having excellent mechanical properties such as high bending strength and impact strength.

1 is a graph showing the tensile strength evaluation results of Examples and Comparative Examples.
Fig. 2 is a graph showing the elongation percentage evaluation results of Examples and Comparative Examples. Fig.
3 is a graph showing the results of evaluating the flexural modulus of Examples and Comparative Examples.
Fig. 4 is a graph showing the degree of improvement of the embodiment versus the comparative example 1. Fig.
5 is a graph showing the intrinsic viscosity evaluation results of Examples and Comparative Examples.
FIG. 6 is a graph showing the degree of improvement of the embodiment versus the comparative example 1. FIG.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  And Comparative Example  : Polymerization of polyethylene resin]

Molecular weight polyethylene resin prepared in the slurry process in the presence of a titanium-based Ziegler-Natta catalyst having a HLMFR of 5 g / 10 min and a density of 0.951 g / cm < 3 > And an antioxidant.

* HLMFR is a high load melt flow index, measured at 190 ° C and 21.6 kg load according to ISO 1133.

(Unit: ppm) Irganox1010 Alkanox® 240 Chimassorb® 944 Tinuvin®770 Cyasorb®3346 Example 1 400 400 900 900 Example 2 1000 1000 900 900 Example 3 1500 1000 900 900 Comparative Example 1 400 400 900 900 Comparative Example 2 400 400

* Irganox® 1010, Alkanox® 240, Chimassorb® 944, Tinuvin® 770, and Cyasorb® 3346 were purchased from Ciba Inc.

[ Experimental Example  One: Example  And In the comparative example  Property analysis of synthesized polyethylene resin]

The physical properties of the polyethylene resins synthesized in the above Examples and Comparative Examples were measured using the following conditions, and the results are shown in Table 2 below.

Melt index: ASTM D 1238

l Density: ASTM D 1525

l Tensile strength and elongation: ASTM D 683

l Flexural modulus: ASTM D 790

l IZOD impact strength: ASTM D 256

l Surface hardness: ASTM D 785

Analysis of the physical properties of the polyethylene resins of Examples and Comparative Examples Test Items unit Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Melt index 190 ℃
(2.16 / 21.6 kg) g / 10 min 0.05 / 5.9 0.03 / 4.7 0.03 / 4.7 0.03 / 5.0 0.03 / 4.8 density g / cm3 0.950 0.949 0.950 0.949 0.949 Tensile strength (yield point) Kg / cm2 239 215 220 230 215 Breaking point elongation % > 500 > 500 > 500 > 500 > 500 Flexural modulus Kg / cm2 12,000 12,200 12,400 12,000 12,100 IZOD impact strength
(23 ° C) Kg · cm / cm NB NB NB NB NB IZOD impact strength
(-30 ° C) Kg · cm / cm 40 42 40 42 42 Surface hardness R 57 57 58 56 57

[ Experimental Example  2: Analysis of long term durability properties of biodiesel]

The polyethylene resin synthesized in each of Examples and Comparative Examples was prepared as a sample and precipitated in biodiesel B30. The tensile strength, elongation, and flexural modulus at a temperature of 70 ° C for 3,000 hours were evaluated and shown in FIGS. 1 to 4 . The evaluation conditions are the same as described above.

[ Experimental Example  3: Long term for biodiesel Intrinsic viscosity  Change analysis]

A polyethylene container having a thickness of 0.8 mm and a volume of 500 ml was molded from the polyethylene resin synthesized in each of Examples and Comparative Examples to fill the biodiesel B30 and then the change in intrinsic viscosity at a temperature of 80 DEG C for 2,500 hours was evaluated. 6.

[ Example  And Comparative example  compare]

As shown in Table 1, the polyethylene resin and polyethylene resin containers of Examples and Comparative Examples were prepared by changing the kind and content of the stabilizer and the antioxidant under the same conditions. In Examples 1 to 3, 900 ppm of Tinuvin770 and 900 ppm of Cyasorb3346 were added, respectively, and the content or content ratio of phenol antioxidant and phosphorus antioxidant was added differently. Comparative Example 1 was prepared in the same manner as in Example 1 except that Chimassorb®944 was added instead of Cyasorb®3346, and Comparative Example 2 was prepared by adding only an antioxidant without adding a stabilizer.

As shown in Table 2, the polyethylene resins of Examples 1 to 3 had the same melt index, density, tensile strength (yield point), breaking point, elongation, flexural modulus, IZOD impact strength, It can be confirmed that the tensile strength, elongation, flexural modulus and the like are excellent, so that the processability of the polyethylene storage container is excellent.

As shown in the Experimental Examples 2 and 3 and the figures, the polyethylene resin of Examples 1 to 3 and the storage container prepared by using the polyethylene resin of Examples 1 to 3, even after being precipitated in biodiesel or filled with biodiesel, The rate of change of the mechanical properties of the flexural modulus and the rate of change of the intrinsic viscosity are low and it is confirmed that the durability against biodiesel is excellent.

More specifically, according to Fig. 1, the polyethylene resin of the above example is much lower than the 7.1% of Comparative Example 1 at a change rate of the tensile strength at 500 hours of less than 3%, and the rate of change of the tensile strength for 3000 hours is also conducted It can be confirmed that the polyethylene resin of the comparative example is particularly small as compared with the comparative example 1.

2 and 3, it can be confirmed that the polyethylene resin of the above example shows a smaller change rate than that of the polyethylene resin of the comparative example. This indicates that the polyethylene resin of the examples significantly improved the tensile strength, the elongation and the flexural modulus as compared with the comparative example 1, especially from the comparative physical property chart of Comparative Example 1 of Fig.

As shown in Figs. 5 and 6, examples of changes in intrinsic viscosity after filling the biodiesel with the storage container prepared using the polyethylene resin of the above-mentioned examples and comparative examples were small, It can be confirmed that it has a remarkably improved intrinsic viscosity.

Claims (12)

Polyethylene resin; A stabilizer comprising a first hindered amine compound and a second hindered amine compound comprising a repeating unit represented by Formula 1 below; And an antioxidant,
A polyethylene storage container for biodiesel having a rate of change in tensile strength of 3% or less according to ASTM D 683 before and after 500 hours of precipitation in biodiesel (B30) at 70 캜;
[Chemical Formula 1]

The method according to claim 1,
Wherein said first hindered amine compound has a weight average molecular weight of 1,500 to 10,000 g / mol.
The method according to claim 1,
Wherein said second hindered amine compound has a weight average molecular weight of less than or equal to 500 g / mol.
The method according to claim 1,
Wherein the first hindered amine compound and the second hindered amine compound are added in a molar ratio of 2: 1 to 1: 2.
The method according to claim 1,
Wherein said second hindered amine compound is selected from the group consisting of bis- (2,2,6,6-tetramethyl-4-piperidinyl) -secarate, 2,2,6,6-tetramethylpiperidine, 6,6-tetramethylpiperidin-4-ol, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin- , 2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 2,2,6,6-tetramethylpiperidin-4-yl stearate, 2,2,6 Tetramethylpiperidine-4-yl benzoate, 2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butylbenzoate, bis (2,2,6,6- Tetramethylpiperidin-4-yl) succinate, bis (2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (2,2,6,6- (2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis (2,2,6,6-tetramethylpiperidin- 4-yl) isophthalate, bis (2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis (2,2,6,6- N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) adipinamide, N- (2,2,6,6-tetramethylpiperidin- , 6,6-tetramethylpiperidin-4-yl) caprolactam, N- (2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide, 2,4,6 (2,2,6,6-tetramethylpiperidin-4-yl)] - s-triazine, 4,4'-ethylene bis (2,2,6,6- Tetramethylpiperazin-3-one) tris (2,2,6,6-tetramethyl-1-oxylpiperidin-4-yl) phosphite, their N-hydroxy derivatives and N-oxyl derivatives ≪ RTI ID = 0.0 > 1, < / RTI >
The method according to claim 1,
The antioxidant may be a phenolic antioxidant; And a phosphorus-based antioxidant.
The method according to claim 6,
Wherein the phenolic antioxidant is selected from the group consisting of 3 - {[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyl] oxy} -2,2- propyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoate, benzenepropanoic acid 3,5-bis (1,1- dimethylethyl) - Hydroxy-2,2-bis [[3- [3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] -1- oxopropoxy] methyl] (1,1-dimethylethyl) -4-hydroxyoctadecyl ester, 4 - [[4,6-bis (octylthio) -1,3,5-triazine Yl] amino] -2,6-bis (1,1-dimethylethyl) phenol, and N, N'-hexamethylenebis (3,5-di- tert.butyl- Meade). ≪ / RTI >
The method according to claim 6,
The phosphorus antioxidant may be at least one selected from the group consisting of tris (2,4-ditert-butylphenyl) phosphate, 2,4-bis (1,1-dimethylethyl) phenol phosphite, and phosphorous [1,1'- -Di-bis-, tetrakis [2,4-bis (1,1-dimethylethyl) phenyl] ester.
The method according to claim 6,
Wherein the antioxidant comprises the phenolic antioxidant and the phosphorus antioxidant in a molar ratio of 2: 1 to 1: 2.
The method according to claim 1,
Wherein a rate of change of intrinsic viscosity before and after filling biodiesel (B30) at 80 DEG C for 2500 hours is 40% or less.
The method according to claim 1,
Wherein the polyethylene resin is an ethylene homopolymer or a copolymer of ethylene and an? -Olefin.
12. The method of claim 11,
Wherein the? -Olefin comprises at least one monomer selected from the group consisting of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, Storage container.

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