KR102003595B1 - Modified polymer composition and stabilizer mixture for making the same - Google Patents

Abstract

Disclosed is a stabilizer mixture for modifying olefinic polymers, comprising at least one organic phosphorus-containing antioxidant represented by the formula selected from the group consisting of formulas 1, 2, 3, 4, 5, 6, 7 and 8; and one or more sulfur-containing carboxylate salts represented by the formula selected from the group consisting of formulas 9, 10, 11 and 12. Also, disclosed herein is a modified polymer composition prepared from olefinic polymers using the stabilizer mixture. The olefinic polymer is selected from the group consisting of polyolefins, ethylene-vinyl acetate copolymers and combinations thereof.

Description

MODIFIED POLYMER COMPOSITION AND STABILIZER MIXTURE FOR MAKING THE SAME [0002]

The present invention relates to a modified polymer composition prepared from an olefinic polymer using a modified polymer composition, more particularly a mixture of a stabilizer containing at least one organophosphorous-containing antioxidant and at least one sulfur-containing carboxylate salt .

Olefin based polymers such as polyolefins and ethylene-vinyl acetate copolymers are widely used in the manufacture of various products because they are non-toxic and easily processed with excellent chemical stability, mechanical strength, electrical insulation and dimensional stability. However, olefinic polymers have disadvantages such as sensitivity to discoloration (e.g., yellowing) and reduced mechanical properties due to degradation by oxidation caused by heat, light and oxygen.

It is widely known that the use of an antioxidant in the step of producing a molded article from an olefinic polymer prevents the olefinic polymer from being deteriorated by oxidation, thereby improving the mechanical properties and heat resistance of the olefinic polymer. However, the use of antioxidants may cause coloration of the olefinic polymer and reduced processing stability. Further, in the step of producing a molded article from the olefin-based polymer, the use of an anti-acid agent can suppress deterioration of the olefin-based polymer by the acidic component. However, antacids can cause coloration of the olefinic polymer and reduced processing stability.

According to a first aspect of the present application, there is provided an antioxidant composition comprising at least one organic phosphorus-containing antioxidant represented by the formula selected from the group consisting of the following formulas 1, 2, 3, 4, 5, 6, And at least one sulfur-containing carboxylate salt represented by the formula selected from the group consisting of 11, 12, and 12:

Wherein R ¹¹ , R ¹² and R ¹³ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

Wherein R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group And Z ⁴¹ and Z ⁴² are independently selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups.

Wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, Z ⁵¹ is selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups.

로 표시되는 기로 이루어진 군으로부터 선택되며, R⁶⁵, R⁶⁶ 및 R⁶⁷은 수소, 3급-부틸기, 이소프로필페닐기 및 선형 C₁-C₈ 알킬기로 이루어진 군으로부터 독립적으로 선택되고, Z⁶¹은 O, S 및 C₁-C₄ 알킬렌기로 이루어진 군으로부터 선택된다.]Wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, T is C ₁ -C ₁₈ hydrocarbon group and

R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, and Z ⁶¹ is selected from the group consisting of O, S and C ₁ -C ₄ alkylene groups.

Wherein R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group . ≪ / RTI >

Wherein R ⁹¹ is selected from the group consisting of hydrogen and C ₁ -C ₁₈ alkyl groups, R ⁹² is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, M ^{q +} is Ca ^{2 +} , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ and Al ³⁺ , q is an integer of 2 or 3, and t is an integer of 0 to 6.]

Wherein X ¹¹ and X ¹² are independently selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ¹¹ and Y ¹² are independently selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₃₀ alkyl groups, C ₁₈ aryl group, and a and b are independently an integer of 1 to 6.

를 나타내고, c 및 d는 독립적으로 1 내지 6의 정수이고, p는 1 내지 9의 정수이나, 단 p가 2 이상의 정수일 때 복수개의 G¹은 동일하거나 상이하고 복수개의 X²¹은 동일하거나 상이하다.]Wherein X ²¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , G ¹ and G ² are independently selected from the group consisting of

C and d are independently an integer of 1 to 6, p is an integer of 1 to 9, provided that when p is an integer of 2 or more, plural G ^{1 s} are the same or different and plural X ^{21 s} are the same or different .]

X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ³¹ is a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and R ⁹³ OOC- (CH ₂ ) _k -, R ⁹³ is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, and k is an integer of 1 to 5. ]

According to a second aspect of the invention, there is provided a modified polymer composition prepared from an olefinic polymer using the stabilizer mixture described above. The olefinic polymer is selected from the group consisting of a polyolefin, an ethylene-vinyl acetate copolymer, and combinations thereof.

The present invention provides a stabilizer mixture for modifying olefinic polymers, comprising at least one organophosphorous-containing antioxidant and at least one sulfur-containing carboxylate salt.

According to the present application, one or more organic phosphorus-containing antioxidants are represented by chemical formulas selected from the group consisting of chemical formulas 1, 2, 3, 4, 5, 6, 7 and 8 shown below. The organophosphorus-containing antioxidant in the non-oxidizing and stabilizing mixture may be selected from the group consisting of an organophosphorus-containing antioxidant of formula (1), an organophosphorus-containing antioxidant of formula (2), an organophosphorus-containing antioxidant of formula Containing organic antioxidant, organic phosphorus-containing antioxidant of Formula 5, organophosphorus-containing antioxidant of Formula 6, organophosphorus-containing antioxidant of Formula 7, organophosphorus-containing antioxidant of Formula 8, and combinations thereof Lt; / RTI >

The organic phosphorus-containing antioxidant represented by the formula (1) is as follows:

Formula 1

Wherein R ¹¹ , R ¹² and R ¹³ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

The organic phosphorus-containing antioxidant represented by the general formula (2) is as follows:

(2)

Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

The organic phosphorus-containing antioxidant represented by the general formula (3) is as follows:

(3)

Wherein R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group.

The organic phosphorus-containing antioxidant represented by the general formula (4) is as follows:

Formula 4

Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group And Z ⁴¹ and Z ⁴² are independently selected from the group consisting of O, S and C ₁ -C ₄ alkylene groups.

The organic phosphorus-containing antioxidant represented by the general formula (5) is as follows:

Formula 5

Wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, and Z ⁵¹ is selected from the group consisting of O, S and C ₁ -C ₄ alkylene groups.

The organic phosphorus-containing antioxidant represented by the general formula (6) is as follows:

6

로 표시되는 기로 이루어진 군으로부터 선택되며, R⁶⁵, R⁶⁶ 및 R⁶⁷은 수소, 3급-부틸기, 이소프로필페닐기 및 선형 C₁-C₈ 알킬기로 이루어진 군으로부터 독립적으로 선택되고, Z⁶¹은 O, S 및 C₁-C₄ 알킬렌기로 이루어진 군으로부터 선택된다.Wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, T is C ₁ -C ₁₈ Hydrocarbon group and

R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, and Z ⁶¹ is selected from the group consisting of O, and S are selected from the group consisting C ₁ -C ₄ alkylene.

The organic phosphorus-containing antioxidant represented by the general formula (7) is as follows:

Formula 7

Wherein R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group It is selected independently.

The organic phosphorus-containing antioxidant represented by the general formula (8) is as follows:

8

According to the present application, at least one sulfur-containing carboxylate salt is represented by the formula selected from the group consisting of the following formulas (9), (10), (11) In other words, the sulfur-containing carboxylate salt in the stabilizer mixture can be selected from the group consisting of a sulfur-containing carboxylate salt of formula (9), a sulfur-containing carboxylate salt of formula (10), a sulfur-containing carboxylate salt of formula Carboxylate salts, and combinations thereof.

The sulfur-containing carboxylate salt represented by the formula (9) is as follows:

Formula 9

Wherein R ⁹¹ is selected from the group consisting of hydrogen and C ₁ -C ₁₈ alkyl groups, R ⁹² is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, M ^{q +} is Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ and Al ³⁺ , q is an integer of 2 or 3, and t is an integer of 0 to 6.

The sulfur-containing carboxylate salt represented by formula (10) is as follows:

10

Wherein X ¹¹ and X ¹² are independently selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ¹¹ and Y ¹² are independently selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl group, and a and b are independently an integer of 1 to 6.

The sulfur-containing carboxylate salt represented by the formula (11) is as follows:

Formula 11

를 나타내고, c 및 d는 독립적으로 1 내지 6의 정수이고, p는 1 내지 9의 정수이나, 단 p가 2 이상의 정수일 때 복수개의 G¹은 동일하거나 상이하고 복수개의 X²¹은 동일하거나 상이하다.Wherein X ²¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , G ¹ and G ² are independently selected from the group consisting of

C and d are independently an integer of 1 to 6, p is an integer of 1 to 9, provided that when p is an integer of 2 or more, plural G ^{1 s} are the same or different and plural X ^{21 s} are the same or different .

The sulfur-containing carboxylate salt represented by formula (12) is as follows:

Formula 12

Wherein X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ³¹ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and R ⁹³ OOC - (CH ₂ ) _k -, R ⁹³ is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, and k is an integer of 1 to 5.

The present application also provides modified polymer compositions prepared from olefinic polymers using the stabilizer mixtures described above.

Additional details of mixtures of olefinic polymers and stabilizers according to the present disclosure are described below.

Olefin polymer :

Suitable olefinic polymers herein are selected from the group consisting of polyolefins, ethylene-vinyl acetate copolymers, and combinations thereof.

Stabilizer mixture :

Examples of the organic phosphorus-containing antioxidant represented by Chemical Formula 1 include tris (2,4-di-tert-butylphenyl) phosphite (antioxidant 168), triphenylphosphite, tris (4- ) Phosphite, tris (nonylphenyl) phosphite, and tris (p-cumylphenyl) phosphite.

Examples of the organic phosphorus-containing antioxidant represented by the general formula (2) include bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626), 3,9- Phenoxy) -2,4,8,10-tetraoxatetradecane-3,9-diphosphaspiro [5.5] undecane (antioxidant 9228), diphenyl pentaerythritol diphosphite, 10-tetraoxa-3, 9-diphospaspiro [5.5] undecane.

(CAS 번호 161717-32-4), 2-[2,4-비스(1,1-디메틸에틸)페녹시]-5,5-디메틸-1,3,2-디옥사포스포리난, 2,4-디쿠밀페닐 2-부틸-2-에틸-1,3-프로판디올 포스파이트, 및 2-[2,4-비스(1,1-디메틸에틸)페녹시]-5-부틸-5-에틸-1,3,2-디옥사포스포리난을 포함하지만 이들로 한정되지는 않는다. Examples of the organic phosphorus-containing antioxidant represented by the general formula (3) include

(CAS No. 161717-32-4), 2- [2,4-bis (1,1-dimethylethyl) phenoxy] -5,5-dimethyl-1,3,2-dioxaphosphorinane, Butyl-2-ethyl-1,3-propanediol phosphite and 2- [2,4-bis (1,1-dimethylethyl) phenoxy] -1,3,2-dioxaphosphorinone. ≪ / RTI >

(CAS 번호 1601458-04-1)이다.Non-limiting examples of organophosphorous-containing antioxidants represented by formula

(CAS No. 1601458-04-1).

(CAS 번호 205518-79-2)이다.Non-limiting examples of the organic phosphorus-containing antioxidant represented by the general formula

(CAS No. 205518-79-2).

Examples of the organic phosphorus-containing antioxidant represented by the formula (6) include 2,4,8,10-tetra-tert-butyl-6- [(2- ethylhexyl) oxy] [1,3,2] dioxaphosphosine (HP-10), 2,2'-thiobis [6-tert-butyl-p-cresol] cyclic monophenyl phosphite, and 2,2'- (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite.

Examples of the organic phosphorus-containing antioxidant represented by the formula (7) include antioxidants P-EPQ, aposphonic acid, [1,1'-biphenyl] -4,4'-diyl bis-, tetrakis [2- , 1-dimenylethyl) phenyl] esters, and aposulfonic acid, [1,1'-biphenyl] -4,4'-diyl bis-, tetraphenyl ester.

In certain embodiments, R ⁹¹ is hydrogen and R ⁹² is selected from the group consisting of C ₁ -C ₁₈ alkyl groups and C ₆ -C ₁₈ aryl groups. The term "aryl group" refers to an unsubstituted aryl group, a hydrocarbon-substituted aryl group, or an aryl-substituted hydrocarbon group. In certain embodiments, R ⁹² is dodecyl. Examples of the sulfur-containing carboxylate salt represented by the formula (9) include (C ₁₂ H ₂₅ SCH ₂ COO) ₂ Zn, (C ₁₂ H ₂₅ SCH ₂ COO) ₂ Ca, (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₂ Zn , (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₂ Ca, and (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₃ Al.

In certain embodiments, X ¹¹ and X ¹² are independently selected from the group consisting of Ca ²⁺ and Zn ²⁺ , and Y ¹¹ and Y ¹² are independently selected from the group consisting of -C ₇ H ₁₅ and -C ₁₇ H ₃₅ Is selected. Examples of the sulfur-containing carboxylate salt represented by the formula (10) include

But are not limited to these.

이고, c 및 d는 독립적으로 1 또는 2이다. 화학식 11로 표시되는 황-함유 카복실레이트 염의 예는

In certain embodiments, X ²¹ is selected from the group consisting of Ca ²⁺ and Zn ²⁺ , and G ¹ and G ² are independently selected from the group consisting of

And c and d are independently 1 or 2. Examples of the sulfur-containing carboxylate salt represented by the formula (11) include

But are not limited to, where p is an integer from 1 to 9, inclusive.

을 포함하지만 이들로 한정되지는 않는다.Examples of the sulfur-containing carboxylate salt represented by the formula (12) include

But are not limited to these.

The ratio of the organic phosphorus-containing antioxidant to the sulfur-containing carboxylate salt is from 1:99 to 99: 1.

According to the present application, the stabilizer mixture may further comprise an antioxidant selected from the group consisting of a hindered phenolic antioxidant, a benzofuranone antioxidant, an amine oxide antioxidant, and combinations thereof.

Examples of hindered phenolic antioxidants include pentaerythritol tetra- [beta - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], ethylene bis (oxyethylene) bis [ - (3- tert -butyl-4-hydroxy-5-methylphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5- Butyl (4-hydroxybenzyl) isocyanurate, tris (butylcresol) butane, 4,4'- Butyl 3-methylphenol), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydra (4-methyl-4-hydroxyphenyl) propionyl] hexamethylenediamine, 2,2'-methylenebis- (4-methyl- Butyl-4-hydroxy-hydrocinnamate, 1,2-di [- (3,5-di-tert- butylphenol), octyl- Hydroxyphenyl) propionyl] hydrazide, and 2,2'-oxamidobis [ethyl-3- (3,5-di- Id include hydroxyphenyl) propionate], but are not limited to these. Suitable hindered phenolic antioxidants may be used alone or in combination with other suitable hindered phenolic antioxidant (s).

Examples of the benzofuranone-based antioxidant include xylyl dibutylbenzofuranone, 5- (tert-butyl) -3- [5- (tert-butyl) -2-hydroxyphenyl] benzofuran- (CAS No. 214354-68-4), and 3- [3,5-bis (1,1-dimethylethyl) -2-hydroxyphenyl] -5,7-bis , 1-dimethylethyl) -2 (3H) -benzofuranone (CAS No. 210709-72-1). Suitable benzofuranone antioxidants may be used alone or in combination with other suitable benzofuranone antioxidant (s).

Examples of amine oxide-based antioxidants include, but are not limited to, oxidized bis (hydrogenated tallowalkyl) amine and bis (octadecyl) hydroxylamine. Suitable amine oxide antioxidants may be used alone or in combination with other suitable amine oxide antioxidant (s).

According to the present application, the stabilizer mixture may further comprise additives selected from the group consisting of antacids, metal deactivators and combinations thereof.

Antacids can be used to balance the pH of the modified polymer composition and make the antioxidant (s) and sulfur-containing carboxylate salt (s) used more compatible and fatty acid salts. Exemplary fatty acid salts include, but are not limited to, calcium stearate, zinc stearate, magnesium docosate, magnesium stearate, sodium ricinoleate, and potassium palmitate. Suitable fatty acid salts can be used alone or in combination with other suitable fatty acid salt (s).

The metal deactivator can prevent the properties of the modified polymer composition from deteriorating. Exemplary metal deactivators include, but are not limited to, oxalyl-bis (benzylidene) hydrazide. Suitable commercially available metal deactivators include, but are not limited to, Eastman Inhibitor OABH.

In certain embodiments, the stabilizer mixture is present in an amount of 0.01 to 2.2 parts by weight based on 100 parts by weight of the olefinic polymer. The method of preparing the modified polymer composition of the present invention is not limited. For example, a modified polymer composition can be prepared by mixing an olefinic polymer with a stabilizer mixture.

The subsequent processing method of the modified polymer composition is not limited. Any conventional process for molding polyolefins and ethylene-vinyl acetate copolymers can be used. Examples of the molding process include, but are not limited to, extrusion molding, injection molding, and the like.

Hereinafter, an embodiment of the present invention will be described. It is to be understood that these embodiments are for purposes of illustration and description and are not to be construed as limiting the present invention.

Reagents used in the following examples :

1. Polypropylene: B8001, commercially available from Formosa Chemicals & Fibre Corp., referred to as PP in Tables 1 and 2;

2. Polyethylene: LH608M, commercially available from USI Corporation (Taiwan), referred to as PE in Tables 1 and 2;

3. Tris (2,4-di-tert-butylphenyl) phosphite (antioxidant 168): Examples of organic phosphorus-containing antioxidants represented by the formula (1) referred to as A1 in Tables 1 and 2;

4. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626): Examples of organic phosphorus-containing antioxidants represented by the general formula (2) referred to as A2 in Tables 1 and 2 ;

5. 5,9 undecane (antioxidant 9228): 3,9-bis (2,4-cumylphenoxy) -2,4,8,10-tetraoxatetradecane- And examples of the organic phosphorus-containing antioxidant represented by the general formula (2), which is referred to as A3 in 2;

6. 2,4,8,10-Tetra-tert-butyl-6- [(2-ethylhexyl) oxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphosine HP-10): Examples of organic phosphorus-containing antioxidants represented by formula (6), referred to as A4 in Tables 1 and 2;

7. Antioxidant P-EPQ:

: 표 1 및 2에서 A5로 일컬어지는, 화학식 7로 표시되는 유기 인-함유 산화방지제의 예;

: Examples of organic phosphorus-containing antioxidants represented by the general formula (7), referred to as A5 in Tables 1 and 2;

8. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10 oxide (DOPO): an organic phosphorus-containing antioxidant, designated as A6 in Tables 1 and 2,

(CAS 번호 161717-32-4): 표 1 및 2에서 A7로 언급되는, 화학식 3으로 표시되는 유기 인-함유 산화방지제의 예;9.

(CAS No. 161717-32-4): Examples of organic phosphorus-containing antioxidants represented by the general formula (3) referred to as A7 in Tables 1 and 2;

(CAS 번호 205518-79-2): 표 1 및 2에서 A8로 일컬어지는, 화학식 5로 표시되는 유기 인-함유 산화방지제의 예; 10.

(CAS No. 205518-79-2): Examples of organic phosphorus-containing antioxidants represented by the formula (5), referred to as A8 in Tables 1 and 2;

(CAS 번호 1601458-04-1): 표 1 및 2에서 A9로 일컬어지는, 화학식 4로 표시되는 유기 인-함유 산화방지제의 예;11.

(CAS No. 1601458-04-1): Examples of organic phosphorus-containing antioxidants represented by the formula (4), referred to as A9 in Tables 1 and 2;

12. (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₂ Ca: Examples of the sulfur-containing carboxylate salt represented by the formula (9), referred to as B1 in Tables 1 and 2;

13. (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₃ Al: Examples of the sulfur-containing carboxylate salt represented by the formula (9), referred to as B2 in Tables 1 and 2;

: 표 1 및 2에서 B3로 언급되는, 화학식 10으로 표시되는 황-함유 카복실레이트 염의 예;14.

: Examples of the sulfur-containing carboxylate salts represented by the formula (10), referred to as B3 in Tables 1 and 2;

: 표 1 및 2에서 B4로 언급되는, 화학식 11로 표시되는 황-함유 카복실레이트 염의 예;15.

: Examples of the sulfur-containing carboxylate salt represented by the formula (11), referred to as B4 in Tables 1 and 2;

: 표 1 및 2에서 B5로 언급되는, 화학식 12로 표시되는 황-함유 카복실레이트 염의 예; 및16.

: Examples of the sulfur-containing carboxylate salt represented by the formula (12), referred to as B5 in Tables 1 and 2; And

17. distearyl thiodipropionate: referred to as DSTDP.

Examples 1 to 18 :

In each of Examples 1 to 16, 100 parts by weight of polypropylene was uniformly mixed with the amount of the stabilizer mixture shown in Table 1 at 25 DEG C to prepare the modified polymer composition of the present invention. In each of Examples 17 and 18, 100 parts by weight of polyethylene were uniformly mixed with the stabilizer mixture in the amounts indicated in Table 1 at 25 DEG C to prepare the modified polymer composition of the present invention.

Controls 1 to 21 :

In each of the Control Examples 1 to 17, 20 and 21, 100 parts by weight of polypropylene was mixed with the stabilizer (s) in the amounts shown in Table 2 (i.e., organic phosphorus-containing antioxidant alone, sulfur- containing carboxylate ester alone, A sulfur-containing carboxylate salt alone, or a combination of an organic phosphorus-containing antioxidant and a sulfur-containing carboxylate ester) to prepare a modified polymer composition. In each of Controls 18 and 19, a modified polymer composition was prepared by uniformly mixing 100 parts by weight of polyethylene with a stabilizer (i.e., organic phosphorus-containing antioxidant alone) at 25 DEG C in an amount as shown in Table 2.

Evaluation test :

Two-Axis Extruder [Model No. PSM20A, Sino-Alloy Machinery Inc.); The modified polymer composition prepared in Examples 1 to 18 and the Comparative Examples 1 to 21 was extruded using a twin-screw extruder at a temperature of 190 to 230 占 폚, an extruder axial speed of 200 rpm, and a feed rate of 6 rpm, Dried, pelletized and oven dried. Thus, a specimen was prepared. The specimens were further processed repeatedly by extrusion, cooling, air-drying, pelletizing and oven-drying steps to evaluate changes in yellowness and melt index after several runs. The smaller the change in yellowness of the specimen, the better the color stability of the specimen. Similarly, the smaller the change in the melt index of a specimen, the better the processing stability of the specimen.

1. Difference in yellowness (Δb ^* )

For each of the specimens of the modified polymer compositions prepared in Examples 1 to 18 and Controls 1 to 21, using a spectrophotometer (ColorQuest XE manufactured by HunterLab), a third extrusion process The difference in yellowness (Δb ^* ) between the yellowness of the sample obtained after the first extrusion process and the yellowness degree of the sample obtained after the first extrusion process was determined. Similarly, for each of the specimens of the modified polymer compositions prepared in Examples 1 to 18 and Controls 1 to 21, the specimen obtained after the fifth extrusion process was measured using a spectrophotometer (Color Quest XE manufactured by Hunter Lab) ([Delta] b ^* ) between the yellow color of the sample and the yellowness of the sample obtained after the first extrusion process. The results are shown in Tables 3 and 4.

2. Melting Index Difference (ΔMI)

For each of the specimens of each of the modified polymer compositions prepared in Examples 1 to 18 and Controls 1 to 21, using a Laboratory Melt Indexer LMI D4004 manufactured by Dynisco, The melt index difference (? MI) between the melt index of the sample obtained after the extrusion process and the melt index of the sample obtained after the first extrusion process was determined. Likewise, for each of the modified polymer compositions prepared in Examples 1 to 18 and Controls 1 to 21, the labolatory melt indexer LMI D4004 manufactured by Dynesco was used to melt the specimen obtained after the fifth extrusion process (? MI) between the index and the melt index of the sample obtained after the first extrusion process. The melt index difference is defined as the ratio of the melt index of the sample obtained after the individual subsequent extrusion process (third or fifth) to the melt index of the sample obtained after the first extrusion process. The results are shown in Tables 3 and 4.

As shown in Tables 3 and 4, in the case of the specimens E1 to E18 prepared from the modified polymer compositions of Examples 1 to 18, the Δb ^* values of the specimen after the third extrusion process were both 2.88 or less, and after the fifth extrusion process All the Δb ^* values of the specimen are 5.04 or less. However, in the case of the specimens CE1 to CE21 prepared from the modified polymer compositions of Comparative Examples 1 to 21, the Δb ^* values of the specimen after the third extrusion process were all at least 3.12 and the Δb ^* value of the specimen after the fifth extrusion process All are above 5.92. Obviously, the modified polymer compositions of Examples 1-18 (made using the stabilizer mixture herein) have improved color stability compared to the modified polymer compositions of Comparative Examples 1-21.

Specifically, specimens E1 and E10 prepared from the modified polymer compositions of Examples 1 and 10 (containing either organic phosphorus-containing antioxidant A1 and sulfur-containing carboxylate salts B1 and B2) Has better color stability than the specimen CE11 prepared from the polymer composition (containing organic phosphorus-containing antioxidant A1 but containing sulfur-containing carboxylate ester DSTDP rather than sulfur-containing carboxylate salt). Thus, sulfur-containing carboxylate salts when used with organic phosphorus-containing antioxidants can indicate that the modified polymer composition can act synergistically so that it is more resistant to coloring compared to the corresponding sulfur-containing carboxylate ester . Specimen E2 prepared from the modified polymer composition of Example 2 (containing organo-phosphorus-containing antioxidant A2 and sulfur-containing carboxylate salt B1) and modified polymer composition of Comparative Example 12 (organic phosphorus-containing antioxidant A2 But containing sulfur-containing carboxylate ester DSTDP rather than a sulfur-containing carboxylate salt), can be used to derive similar conclusions based on the color stability differences between specimen CE12.

In consideration of processing stability in terms of melt index difference, in the case of the specimens E1 to E16 prepared from the modified polymer compositions (containing PP) of Examples 1 to 16, the ΔMI values of the specimens after the third extrusion process were all 161.58 %, And the ΔMI values of the specimen after the fifth extrusion process are all 258.64% or less. However, in the case of the specimens CE1 to CE17, CE20 and CE21 prepared from the modified polymer compositions (containing PP) of the comparative examples 1 to 17, 20 and 21, the ΔMI values of the specimens after the third extrusion step were all 175.79% And the ΔMI values of the specimen after the fifth extrusion process are all 314.41% or more. Obviously, the modified polymer compositions of Examples 1-16 (made using the stabilizer mixture herein) have improved process stability compared to the modified polymer compositions of Controls 1 to 17, 20 and 21.

Specifically, each of the specimens E1 and E10 prepared from the modified polymer compositions of Examples 1 and 10 (containing the organic phosphorus-containing antioxidant A1 and one of the sulfur-containing carboxylate salts B1 and B2) Has a better process stability than the specimen CE11 prepared from the modified polymer composition (containing organic phosphorus-containing antioxidant Al but containing sulfur-containing carboxylate ester DSTDP rather than sulfur-containing carboxylate salt). Therefore, the sulfur-containing carboxylate salt, when used in combination with an organophosphorous-containing antioxidant, can act synergistically so that the modified polymer composition is more resistant to changes in the melt index compared to the corresponding sulfur- containing carboxylate ester . Specimen E2 prepared from the modified polymer composition of Example 2 (containing organo-phosphorus-containing antioxidant A2 and sulfur-containing carboxylate salt B1) and modified polymer composition of Comparative Example 12 (organic phosphorus-containing antioxidant A2 But containing sulfur-containing carboxylate ester DSTDP rather than a sulfur-containing carboxylate salt), can be derived on the basis of the difference in processing stability between specimen CE12.

Return to specimens E17 and E18 made from the modified polymer compositions of Examples 17 and 18 (containing PE) and to specimens CE18 and CE19 made from the modified polymer compositions (containing PE) of Controls 18 and 19 , The processing stability of the modified polymer composition prepared from PE is described later in terms of melt index difference. However, in evaluating the processing stability, it should be noted that specimens made from PE and specimens made from PP are different due to their characteristic differences (e.g., degree of crosslinking and cracking tendency). Specifically, the MI value of the specimen produced from the PP increases with the number of times the extrusion is performed (i.e., the larger the number of times the extrusion is performed, the larger the ΔMI value), whereas the MI value of the specimen produced from the PE Is generally decreased according to the number of times extrusion is performed (i.e., the larger the number of extrusion is performed, the smaller the value of? MI). Thus, specimens made from PP show satisfactory machining stability if their ΔMI values do not increase sharply with the number of times extrusion is performed, while specimens made from PE show their ΔMI values at the number of times extrusion is performed If not drastically reduced, indicates satisfactory process stability.

In the case of specimens E17 and E18 (manufactured from PE), the ΔMI values of the specimen after the third extrusion process are both 96.06% or more, and the ΔMI values of the specimen after the fifth extrusion process are both 90.15% or more. However, in the case of specimens CE18 and CE19 (manufactured from PE), both the ΔMI value of the specimen after the third extrusion process is 95.11% or less, and the ΔMI value of the specimen after the fifth extrusion process is both 87.33% or less. Obviously, the modified polymer compositions of Examples 17 and 18 (prepared using the stabilizer mixture herein) have improved process stability compared to the modified polymer compositions of Controls 18 and 19. [

In order to further demonstrate the praiseworthy effects of the stabilizer mixture of the present invention, in addition to the above-described processing stability provided by the present stabilizer mixture exemplified by the ΔMI value in Table 3, the modified polymers of Examples 1-18 The MI values of the specimens E1 to E18 prepared from the composition (used to calculate the [Delta] MI value in Table 3) are listed in Table 5. [

The low MI values of the specimens E1 through E16 shown in Table 5 indicate that the stabilizer mixture of the present invention can impart satisfactory physical properties to the polymer composition prepared from PP (i.e., the lower the MI value, And the high MI values of specimens E17 and E18 shown in Table 5 indicate that the stabilizer mixture of the present disclosure can impart satisfactory physical properties to the polymer composition made from PE The higher the physical properties of the polymer composition made from PE). In addition, the following comparisons between specimens made from PP can further demonstrate the effect of the present stabilizer mixture on the physical properties of the polymer composition. Sample CE11 with MI values of 0.3828, 0.6729 and 1.4097 after the first, third and fifth extrusion processes, containing the organophosphorus-containing antioxidant Al but containing the sulfur-containing carboxylate ester DSTDP rather than the sulfur-containing carboxylate salt ), Specimens E1 and E10 (containing either organic phosphorus-containing antioxidant Al and sulfur-containing carboxylate salts B1 and B2) have lower MI values after several extrusion. Likewise, Sample CE12 with an MI value of 0.3616, 0.6534 and 1.1369 after the first, third and fifth extrusion processes (containing the organo phosphorus-containing antioxidant A2 but containing the sulfur-containing carboxylate ester DSTDP rather than the sulfur- (Containing organic phosphorus-containing antioxidant A2 and sulfur-containing carboxylate salt B1) has lower MI values after several extrusion. Therefore, the stabilizer mixture herein not only provides processing stability of the polymer composition, but also imparts satisfactory physical properties to the polymer composition.

In the foregoing description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiment (s). However, those skilled in the art will appreciate that one or more of the other embodiments may be practiced without some of these specific details. Also, throughout this application, it should be understood that reference to "an embodiment," "an embodiment," "an embodiment, or the like in which the order is expressed" means that a particular feature, structure, or characteristic may be included in the practice of the invention. In the detailed description, it is also to be understood that the various aspects sometimes together form a single embodiment, figure, or section in the description to aid in understanding various aspects of the present invention and the subject matter.

Although the present disclosure has been described in connection with what is considered to be the exemplary embodiment (s), it is to be understood that this disclosure is not limited to the disclosed embodiment (s), but is to be accorded the widest scope consistent with the broadest interpretation and scope thereof Are intended to cover various modifications and variations.

Claims (13)

At least one organic phosphorus-containing antioxidant represented by the formula selected from the group consisting of the following formulas 1, 2, 3, 4, 5, 6, 7 and 8,
One or more sulfur-containing carboxylate salts
≪ / RTI >
Wherein the at least one organophosphorus containing antioxidant is represented by the formula selected from the group consisting of the following formulas 2, 3, 4, 5, 6, 7 and 8, 9, 10, 11 and 12,
Wherein said at least one sulfur-containing carboxylate salt is represented by the formula selected from the group consisting of the following formulas (10) and (12), wherein said at least one organophosphorus-containing antioxidant is represented by the formula
Stabilizer mixture for modifying olefinic polymers:
Formula 1

Wherein R ¹¹ , R ¹² and R ¹³ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
(2)

Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
(3)

Wherein R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
Formula 4

Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group And Z ⁴¹ and Z ⁴² are independently selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups,
Formula 5

Wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, Z ⁵¹ is selected from the group consisting of O, S and C ₁ -C ₄ alkylene groups.
6

Wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, T is C ₁ -C ₁₈ hydrocarbon group and

R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, and Z ⁶¹ is selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups.
Formula 7

Wherein R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group Lt; RTI ID = 0.0 >
8

Formula 9

Wherein R ⁹¹ is selected from the group consisting of hydrogen and C ₁ -C ₁₈ alkyl groups, R ⁹² is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, M ^{q +} is Ca ^{2 +} , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ and Al ³⁺ , q is an integer of 2 or 3, and t is an integer of 0 to 6,
10

Wherein X ¹¹ and X ¹² are independently selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ¹¹ and Y ¹² are independently selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₃₀ alkyl groups, C ₁₈ aryl group, and a and b are independently an integer of 1 to 6,
Formula 11

Wherein X ²¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , G ¹ and G ² are independently selected from the group consisting of

C and d are independently an integer of 1 to 6, p is an integer of 1 to 9, provided that when p is an integer of 2 or more, plural G ^{1 s} are the same or different and plural X ^{21 s} are the same or different ]
Formula 12

X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ³¹ is a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and R ⁹³ OOC- (CH ₂ ) _k -, R ⁹³ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, and k is an integer of 1 to 5, . The method according to claim 1,
R ⁹¹ is hydrogen, and R ⁹² is selected from the group consisting of C ₁ -C ₁₈ alkyl groups and C ₆ -C ₁₈ aryl groups. 3. The method of claim 2,
R ⁹² is dodecyl, a stabilizer mixture. The method according to claim 1,
Wherein the stabilizer mixture is selected from the group consisting of a hindered phenolic antioxidant, a benzofuranone antioxidant, an amine oxide antioxidant, and combinations thereof. 5. The method of claim 4,
Wherein the phenolic antioxidant is selected from the group consisting of pentaerythritol tetra- [beta - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], ethylene bis (oxyethylene) bis [ (3-3-butyl-4-hydroxy-5-methylphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (butylcresol) butane, 4,4'- Butyl-3-methylphenol), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazide , N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hexamethylenediamine, 2,2'- Butylphenol), octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 1,2-di [ -Hydroxyphenyl) propionyl] hydrazide, 2,2'-oxamidobis [ethyl-3- (3,5-di- De-hydroxyphenyl) propionate], and the stabilizing agent mixture is selected from the group consisting of. 5. The method of claim 4,
Wherein the benzopyranone antioxidant is selected from the group consisting of xylyl dibutylbenzofuranone, 5- (tert-butyl) -3- [5- (tert-butyl) -2-hydroxyphenyl] benzofuran- (1,1-dimethylethyl) -2 (3H) -benzofuranone, and 3- [3,5-bis (1,1-dimethylethyl) -2-hydroxyphenyl] -5,7- A combination thereof, and combinations thereof. 5. The method of claim 4,
Wherein the amine oxide-based antioxidant is selected from the group consisting of oxidized bis (hydrogenated tallowalkyl) amine, bis (octadecyl) hydroxylamine, and combinations thereof. The method according to claim 1,
Wherein the stabilizer mixture further comprises an additive selected from the group consisting of antacids, metal deactivators, and combinations thereof. 9. The method of claim 8,
Wherein said antacid is a fatty acid salt. 9. The method of claim 8,
Wherein the metal deactivator is oxalyl-bis (benzylidene) hydrazide. An olefin-based polymer selected from the group consisting of polyolefins, ethylene-vinyl acetate copolymers, and combinations thereof, and
At least one organic phosphorus-containing antioxidant represented by the formula selected from the group consisting of the following formulas 1, 2, 3, 4, 5, 6, 7 and 8, and one or more sulfur-containing carboxylate salts Topic mixture
≪ / RTI >
Wherein the at least one organophosphorus containing antioxidant is represented by the formula selected from the group consisting of the following formulas 2, 3, 4, 5, 6, 7 and 8, 9, 10, 11 and 12,
Wherein said at least one sulfur-containing carboxylate salt is represented by the formula selected from the group consisting of the following formulas (9), (10) and (12), wherein said at least one organophosphorus-
Modified polymer composition:
Formula 1

Wherein R ¹¹ , R ¹² and R ¹³ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
(2)

Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
(3)

Wherein R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group,
Formula 4

Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group And Z ⁴¹ and Z ⁴² are independently selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups,
Formula 5

Wherein R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, Z ⁵¹ is selected from the group consisting of O, S and C ₁ -C ₄ alkylene groups.
6

Wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, T is C ₁ -C ₁₈ hydrocarbon group and

R ⁶⁵ , R ⁶⁶ and R ⁶⁷ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group, and Z ⁶¹ is selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups.
Formula 7

Wherein R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ and R ⁷⁸ are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group and a linear C ₁ -C ₈ alkyl group Lt; RTI ID = 0.0 >
8

Formula 9

Wherein R ⁹¹ is selected from the group consisting of hydrogen and C ₁ -C ₁₈ alkyl groups, R ⁹² is selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, M ^{q +} is Ca ^{2 +} , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ and Al ³⁺ , q is an integer of 2 or 3, and t is an integer of 0 to 6,
10

Wherein X ¹¹ and X ¹² are independently selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ¹¹ and Y ¹² are independently selected from the group consisting of C ₁ -C ₃₀ alkyl groups and C ₆ -C ₃₀ alkyl groups, C ₁₈ aryl group, and a and b are independently an integer of 1 to 6,
Formula 11

Wherein X ²¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , G ¹ and G ² are independently selected from the group consisting of

C and d are independently an integer of 1 to 6, p is an integer of 1 to 9, provided that when p is an integer of 2 or more, plural G ^{1 s} are the same or different and plural X ^{21 s} are the same or different ]
Formula 12

X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ and Zn ²⁺ , Y ³¹ is a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and R ⁹³ OOC- (CH ₂ ) _k -, R ⁹³ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, and k is an integer of 1 to 5, . 12. The method of claim 11,
Wherein the stabilizer mixture is present in an amount of 0.01 to 2.2 parts by weight based on 100 parts by weight of the olefinic polymer. 12. The method of claim 11,
Wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and combinations thereof.