JP2018053238A - Modified polymer composition and stabilizer mixture for making the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer mixture for an olefin-based polymer that improves color stability, processing stability and the like.SOLUTION: Disclosed herein is a stabilizer mixture for modifying an olefin-based polymer selected from the group consisting of polyolefin, ethylene-vinyl acetate copolymer and a combination thereof. The stabilizer mixture comprises at least one organic phosphorus-containing antioxidant with a phenoxy group bound to phosphorus, and at least one sulfur-containing carboxylate.SELECTED DRAWING: None

Description

  The present disclosure relates to modified polymer compositions, and more particularly made from olefinic polymers using a stabilizer mixture containing at least one organophosphorus-containing antioxidant and at least one sulfur-containing carboxylate. The modified polymer composition.

  Olefin-based polymers such as polyolefin and ethylene-vinyl acetate copolymer are widely used in the manufacture of various products because they are excellent in chemical stability, mechanical strength, electrical insulation, dimensional stability, non-toxic and easy to process. ing. However, olefinic polymers are disadvantageous in that they tend to discolor (such as yellowing) due to oxidative degradation due to heat, light, oxygen, etc., and the mechanical properties are reduced.

  Therefore, in order to prevent oxidative degradation of the olefin polymer and improve mechanical properties and heat resistance, it is known to use an antioxidant in the process of producing a molded product from the olefin polymer. However, when an antioxidant is used (for example, as described in US Pat. No. 3,856,846, US Pat. No. 3,532,660, US Pat. No. 3,649,690), coloring of the olefin-based polymer and deterioration of processing stability may occur. Further, an oxidation resistant agent can be used in the process of producing a molded product from the olefin polymer so as to suppress the decomposition of the olefin polymer by the acidic substance. Nevertheless, acidic substances (as described, for example, in US Pat. No. 5,728,363) can lead to coloration of the olefinic polymer and reduced processing stability.

U.S. Pat. No. 3,856,846 US Pat. No. 3,532,660 US Pat. No. 3,649,690 US Pat. No. 5,728,363

According to a first aspect of the present disclosure, a stabilizer mixture for modification of olefinic polymers comprising:
At least one organic phosphorus represented by the formula selected from the group consisting of formulas (1), (2), (3), (4), (5), (6), (7) and (8) Containing antioxidants,
There is provided a stabilizer mixture comprising at least one sulfur-containing carboxylate represented by a formula selected from the group consisting of formulas (9), (10), (11) and (12).

Provided that R ¹¹ , R ¹² , and R ¹³ are independently selected from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and linear C ₁ -C ₈ alkyl group;

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

Provided that R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are independently selected from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and linear C ₁ -C ₈ alkyl group;

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

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

However,
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 a C ₁ -C ₁₈ hydrocarbon group, and

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

Provided that R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are hydrogen, tert-butyl group, isopropylphenyl group, and straight-chain C ₁ -C ₈ alkyl group. Selected independently from the group

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

However,
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 a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, and
a and b are each an integer ranging from 1 to 6,

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

Wherein c and d are each integers in the range of 1-6, and
p is an integer in the range of 1 to 9, provided that when p is an integer of 2 or greater than 2, a plurality of G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different. Often,

However,
X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , and Zn ²⁺ , and
Y ³¹ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and a group represented by R ⁹³ OOC— (CH ₂ ) _k —, wherein R ⁹³ is C ₁ -C Selected from the group consisting of ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, k is an integer in the range of 1-5.
Moreover, according to the 2nd aspect of this indication, the modified polymer composition manufactured from an olefin type polymer using the said stabilizer mixture is provided. The olefin polymer is selected from the group consisting of polyolefins, ethylene-vinyl acetate copolymers, and combinations thereof.

  The present disclosure provides a stabilizer mixture for modification of olefinic polymers comprising at least one organophosphorus-containing antioxidant and at least one sulfur-containing carboxylate.

  According to the present disclosure, the at least one organic phosphorus-containing antioxidant comprises the following formulas (1), (2), (3), (4), (5), (6), (7) and It is represented by a formula selected from the group consisting of (8). That is, the organic phosphorus-containing antioxidant in the stabilizer mixture is an organic phosphorus-containing antioxidant of formula (1), an organic phosphorus-containing antioxidant of formula (2), an organic phosphorus-containing antioxidant of formula (3), Organophosphorus-containing antioxidant of formula (4), organophosphorus-containing antioxidant of formula (5), organophosphorus-containing antioxidant of formula (6), organophosphorus-containing antioxidant of formula (7), formula (7) It can be selected from the group consisting of organophosphorus-containing antioxidants 8) and combinations thereof.

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

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

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

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

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

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

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

Provided that R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ are hydrogen, tert-butyl group, isopropylphenyl group, and straight-chain C ₁ -C ₈ alkyl group. 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 formula (5) is as follows.

Provided that R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , and R ⁵⁶ are independently from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and 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 formula (6) is as follows.

Provided that R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ are independently selected from the group consisting of hydrogen, tert-butyl, isopropylphenyl, and linear C ₁ -C ₈ alkyl; C ₁ -C ₁₈ hydrocarbon group and,

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

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

Provided that R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are hydrogen, tert-butyl group, isopropylphenyl group, and straight-chain C ₁ -C ₈ alkyl group. Selected independently from the group

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

  According to the present disclosure, the at least one sulfur-containing carboxylate is represented by a formula selected from the group consisting of the following formulas (9), (10), (11), and (12). That is, the organic phosphorus-containing antioxidant in the stabilizer mixture includes a sulfur-containing carboxylate of the formula (9), a sulfur-containing carboxylate of the formula (10), a sulfur-containing carboxylate of the formula (11), It can be selected from the group consisting of the sulfur-containing carboxylates of 12) and combinations thereof.

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

Provided that R ⁹¹ is selected from the group consisting of hydrogen and a C ₁ -C ₁₈ alkyl group, R ⁹² is selected from the group consisting of a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, and M ^{q +} Is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ , and Al ³⁺ , q is an integer of 2 or 3, and t is an integer in the range of 0-6 It is.
The sulfur-containing carboxylate represented by the formula (10) is as follows.

Provided that 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 C ₁ -C ₃₀ alkyl groups and Independently selected from the group consisting of C ₆ -C ₁₈ aryl groups, and a and b are integers in the range of 1-6.

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

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

Wherein c and d are each an integer in the range of 1-6, and p is an integer in the range of 1-9, provided that p is an integer of 2 or greater than 2, G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different.

  The sulfur-containing carboxylate represented by the formula (12) is as follows.

Provided that X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , and Zn ²⁺ , and Y ³¹ is a C ₁ -C ₃₀ alkyl group or a C ₆ -C ₁₈ aryl group. And R ⁹³ OOC— (CH ₂ ) _k —, wherein R ⁹³ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, k Is selected from the group consisting of groups that are integers in the range of 1-5.

  The present disclosure further provides a modified polymer composition made from an olefinic polymer using the stabilizer mixture.

In the following, further details of olefinic polymers and stabilizer mixtures according to the present disclosure will be described.
Olefin polymer:
Suitable olefinic polymers in the present disclosure are selected from the group consisting of polyolefins, ethylene-vinyl acetate copolymers, and combinations thereof.
Stabilizer mixture:
Examples of organic phosphorus-containing antioxidants represented by formula (1) include, but are not limited to, tris (2,4-di-tert-butylphenyl) phosphite (antioxidant 168), triphenylphosphine Phyto, tris (4-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (p-cumylphenyl) phosphite.

  Examples of the organic phosphorus-containing antioxidant represented by the formula (2) include, but are not limited to, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626), 3,9-bis (2,4-cumylphenoxy) -2,4,8,10-tetraoxatetradecane-3,9-diphosphaspiro [5.5] undecane (antioxidant 9228), diphenylpentaerythritol diphosphite, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane.

  Examples of the organic phosphorus-containing antioxidant represented by the formula (3) are not limited to these,

2- [2,4-Bis (1,1-dimethylethyl) phenoxy] -5,5-dimethyl-1,3,2-dioxaphosphorinane, 2,4-dicumylphenyl-2-butyl-2- Ethyl-1,3-propanediol phosphite, 2- [2,4-bis (1,1-dimethylethyl) phenoxy] -5-butyl-5-ethyl-1,3,2-dioxaphosphorinane It is done.

  Non-limiting examples of organophosphorus-containing antioxidants represented by formula (4)

It is.

  Non-limiting examples of organophosphorus-containing antioxidants represented by formula (5)

It is.

  Examples of the organic phosphorus-containing antioxidant represented by the formula (6) include, but are not limited to, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexyl) oxy]- 12H-dibenzo [d, g] [1,3,2] dioxaphosphocin (HP-10), 2,2′-thiobis [6-tert-butyl-p-cresol] cyclic monophenyl phosphite, 2, 2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite.

  Examples of organic phosphorus-containing antioxidants represented by formula (7) include, but are not limited to, antioxidant P-EPQ, phosphonous acid, [1,1'-biphenyl] -4,4'- And diylbis-, tetrakis [2- (1,1-dimethylethyl) phenyl] ester, phosphonous acid, [1,1′-biphenyl] biphenyl] -4,4′-diylbis-, tetraphenylester.

By way of example, R ⁹¹ represents hydrogen and R ⁹² is selected from the group consisting of a C ₁ -C ₁₈ alkyl group and a C ₆ -C ₁₈ aryl group. The “aryl group” as used herein refers to an unsubstituted aryl group, a hydrocarbon-substituted aryl group, or an aryl-substituted hydrocarbon group. In some embodiments, R ⁹² is dodecyl. Examples of the sulfur-containing carboxylate represented by the formula (9) include, but are not limited to, (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.

By way of example, 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 from the group consisting of —C ₇ H ₁₅ and —C ₁₇ H _35. Independently selected. Examples of the sulfur-containing carboxylate represented by the formula (10) are not limited to these,

Is mentioned.

According to an embodiment, X ²¹ is selected from the group consisting of Ca ²⁺ and Zn ²⁺ , and G ¹ and G ² are respectively

Of which c and d are 1 or 2, respectively. Examples of the sulfur-containing carboxylate represented by the formula (11) are not limited to these,

Of which p is an integer in the range of 1-9.

  Examples of the sulfur-containing carboxylate represented by the formula (12) are not limited to these,

It is.

  The ratio of organophosphorus-containing antioxidant to sulfur-containing carboxylate is in the range of 1:99 to 99: 1.

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

  Examples of hindered phenolic antioxidants include, but are not limited to, pentaerythritol-tetra- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], ethylene bis (oxy Ethylene) bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (butylcresol) butane, 4,4'-butylidenebis (6-tert -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'-methylenebis- (4-methyl-6-tert- Butylphenol), octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 1,2-di [-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazide, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]. Suitable hindered phenolic antioxidants can be used alone or in combination with other suitable hindered phenolic antioxidants.

  Examples of benzofuranone antioxidants include, but are not limited to, xylyldibutylbenzofuranone, 5- (tert-butyl) -3- [5- (tert-butyl) -2-hydroxyphenyl] benzofuran-2 ( 3H) -On (Chemical Information Retrieval Service Agency (CAS) No. 214354-68-4), 3- [3,5-bis (1,1-dimethylethyl) -2-hydroxyphenyl] -5,7-bis (1,1-dimethylethyl) -2 (3H) -benzofuranone (CAS No. 210709-72-1). Suitable benzofuranone antioxidants can be used alone or in combination with other suitable benzofuranone antioxidants.

  Examples of amine oxide antioxidants include, but are not limited to, bis (hydrogenated tallow alkyl) amine, bis (octadecyl) hydroxylamine. Suitable amine oxide antioxidants can be used alone or in combination with other suitable amine oxide antioxidants.

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

  The antacid agent can equilibrate the pH of the denatured polymer component and improve the compatibility of the antioxidant and sulfur-containing carboxylate used, and a fatty acid salt can be used. Examples of fatty acid salts include, but are not limited to, calcium stearate, zinc stearate, magnesium docosanoate, magnesium stearate, sodium ricinoleate, and potassium palmitate. Appropriate chlorine can be used alone or in combination with other suitable fatty acid salts.

  The metal deactivator can prevent the physical properties of the modified polymer composition from deteriorating. Examples of 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 some embodiments, the stabilizer mixture is present in an amount ranging from 0.01 to 2.2 parts by weight per 100 parts by weight of the olefinic polymer. In addition, there is no restriction | limiting in the method of manufacturing the modified polymer composition of this indication. For example, a modified polymer composition can be made by mixing an olefinic polymer with a stabilizer mixture.

  There is no restriction | limiting also in the processing method after manufacture of a modified polymer composition. Any conventional method for molding polyolefins and ethylene-vinyl acetate copolymers can be used. Examples of the molding process include, but are not limited to, extrusion molding and injection molding.

Hereinafter, examples of the present disclosure will be described. It should be understood that these examples are illustrative and illustrative and should not be construed as limiting the present disclosure.
Reagents used in the following examples:
1. Polypropylene: B8001, commercially available from Formosa Chemicals & Fiber Corp. In Tables 1 and 2, this is called PP.
2. Polyethylene: LH608M commercially available from USI Corporation (Taiwan). In Tables 1 and 2, called PE.
3. Tris (2,4-di-tert-butylphenyl) phosphite (antioxidant 168): An example of an organic phosphorus-containing antioxidant represented by the formula (1). In Tables 1 and 2, this is called A1.
4). Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626): an example of an organic phosphorus-containing antioxidant represented by the formula (2). In Tables 1 and 2, this is called A2.
5. 3,9-bis (2,4-cumylphenoxy) -2,4,8,10-tetraoxatetradecane-3,9-diphosphaspiro [5.5] undecane (antioxidant 9228): represented by formula (2) Examples of organic phosphorus-containing antioxidants. In Tables 1 and 2, this is called A3.
6). 2,4,8,10-Tetra-tert-butyl-6-[(2-ethylhexyl) oxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin (HP-10): An example of an organic phosphorus-containing antioxidant represented by formula (6). In Tables 1 and 2, it is called A4.
7). Antioxidant P-EPQ:

An example of an organic phosphorus-containing antioxidant represented by formula (7). In Tables 1 and 2, this is called A5.
8). 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO): an example of an organic phosphorus-containing antioxidant represented by the formula (8). In Tables 1 and 2, it is called A6.
9.

An example of an organic phosphorus-containing antioxidant represented by the formula (3). In Table 1 and Table 2, it is called A7.
10.

An example of an organic phosphorus-containing antioxidant represented by the formula (5). In Table 1 and Table 2, it is called A8.
11.

An example of an organic phosphorus-containing antioxidant represented by formula (4). In Tables 1 and 2, it is called A9.
12 (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₂ Ca: an example of a sulfur-containing carboxylate represented by the formula (9). In Table 1 and Table 2, it is called B1.
13. (C ₁₂ H ₂₅ SCH ₂ CH ₂ COO) ₃ Al: an example of a sulfur-containing carboxylate represented by the formula (9). In Table 1 and Table 2, it is called B2.
14

An example of a sulfur-containing carboxylate represented by the formula (10). In Table 1 and Table 2, it is called B3.
15.

An example of a sulfur-containing carboxylate represented by the formula (11). In Table 1 and Table 2, it is called B4.
16.

: An example of a sulfur-containing carboxylate represented by the formula (12). In Table 1 and Table 2, it is called B5.
17. Distearyl thiodipropionate: named DSTDP.
Examples 1-18:
In each of Examples 1 to 16, a modified polymer composition of the present disclosure was produced by uniformly mixing 100 parts by weight of polypropylene with an amount of the stabilizer mixture shown in Table 1 at 25 ° C. In Examples 17 and 18, 100 parts by weight of polyethylene was uniformly mixed with the stabilizer mixture in the amount shown in Table 1 at 25 ° C. to produce the modified polymer composition of the present disclosure.
Comparative Examples 1 to 21:
In Comparative Examples 1 to 17 and 20 to 21, the stabilizer (that is, the organic phosphorus-containing antioxidant alone, the sulfur-containing carboxylate ester alone, the sulfur-containing carboxylate salt alone, or the organic phosphorus-containing agent is used with respect to 100 parts by weight of polypropylene. A combination of an antioxidant and a sulfur-containing carboxylic acid ester) was mixed at 25 ° C. in the amounts shown in Table 2 to produce a modified polymer composition. In Comparative Examples 18 and 19, a modified polymer composition was produced by uniformly mixing the stabilizer (organophosphorus-containing antioxidant alone) in the amount shown in Table 2 with respect to 100 parts by weight of polyethylene at 25 ° C.
Evaluation test:
The modified polymer compositions produced in Examples 1 to 18 and Comparative Examples 1 to 21 were fed into a twin screw extruder (model number PSM20A, manufactured by SINO-ALLOY MACHINERY INC., Temperature 190 to 230 ° C., extruder screw speed: 200 rpm, supplied. Extrusion at a speed of 6 rpm) followed by cooling, air drying, pelletizing, and oven drying. This produced a sample. This sample was further processed repeatedly in the steps of extrusion, cooling, air drying, pelletizing, and oven drying to evaluate changes in yellowness and melt index after several treatments. The smaller the change in yellowness, the better the color stability of the sample. Similarly, the smaller the change in melt index, the better the processing stability of the sample.
1. Yellowness difference (Δb *)
About the sample of each modified polymer composition produced in Examples 1-18 and Comparative Examples 1-21, the yellowness of the sample obtained after the third extrusion and the yellowness of the sample obtained after the first extrusion Difference (Δb *) was measured using a spectrophotometer (ColorQuest XE, manufactured by HunterLab). Similarly, for the samples of the modified polymer compositions produced in Examples 1 to 18 and Comparative Examples 1 to 21, the yellowness of the sample obtained after the fifth extrusion and the sample obtained after the first extrusion The yellowness difference (Δb *) was measured using a spectrophotometer (ColorQuest XE, HunterLab). The results are shown in Tables 3 and 4.
2. Melt index difference (ΔMI)
About the sample of each modified polymer composition manufactured in Examples 1-18 and Comparative Examples 1-21, the melt index of the sample obtained after the third extrusion and the melt index of the sample obtained after the first extrusion Difference (ΔMI) was measured using a laboratory melt indexer (LMI D4004, manufactured by Dynisco). Similarly, about the sample of each modified polymer composition manufactured in Examples 1-18 and Comparative Examples 1-21, the melt index of the sample obtained after the 5th extrusion process and the sample obtained after the 1st extrusion process The difference in melt index (ΔMI) was measured using a laboratory melt indexer (LMI D4004, manufactured by Dynisco). The difference in melt index is defined as the ratio of the melt index of each sample obtained after the subsequent extrusion (3rd or 5th) to the melt index of the sample obtained after the first extrusion. The results are shown in Tables 3 and 4.

   As shown in Table 3 and Table 4, samples E1 to E18 prepared from the modified polymer compositions of Examples 1 to 18 all have Δb * values of 2.88 or less after the third extrusion. The Δb * values of the samples after the fifth extrusion were all 5.04 or less. On the other hand, the samples CE1 to CE21 prepared from the modified polymer compositions of Comparative Examples 1 to 21 all have a Δb * value of 3.12 or more after the third extrusion, and after the fifth extrusion. All samples had Δb * values of 5.92 or more. The modified polymer compositions of Examples 1-18 (produced using the stabilizer mixture of the present disclosure) have clearly improved color stability compared to the modified polymer compositions of Comparative Examples 1-21. doing.

  In particular, samples E1 and E10 prepared from the modified polymer compositions of Examples 1 and 10 (containing organic phosphorus-containing antioxidant A1 and sulfur-containing carboxylates B1 and B2) are comparative examples. Better color compared to sample CE11 made from 11 modified polymer composition (containing organophosphorus-containing antioxidant A1 but containing sulfur-containing carboxylic acid ester DSTDP rather than sulfur-containing carboxylate) Has stability. Therefore, it is shown that when a sulfur-containing carboxylate is used in combination with an organic phosphorus-containing antioxidant, the modified polymer composition can be made difficult to discolor synergistically compared to the corresponding sulfur-containing carboxylate. Further, sample E2 prepared from the modified polymer composition of Example 2 (containing organic phosphorus-containing antioxidant A2 and sulfur-containing carboxylate B1), and modified polymer composition of Comparative Example 12 (organic phosphorus-containing antioxidant) The same conclusion can be drawn from the difference in color stability with the sample CE12 prepared from the agent A2 but containing the sulfur-containing carboxylic acid ester DSTDP instead of the sulfur-containing carboxylate.

  In consideration of processing stability from the difference in melt index, samples E1 to E16 prepared from the modified polymer compositions of Examples 1 to 16 (containing PP) had a ΔMI value of the sample after the third extrusion process. In all cases, the ΔMI value of the sample after the fifth extrusion process was 258.64% or less. On the other hand, in samples CE1 to CE17 and CE20 to CE21 prepared from the modified polymer compositions of Comparative Examples 1 to 17 and 20 to 21 (containing PP), the ΔMI value of the sample after the third extrusion process is all The ΔMI value of the sample after the fifth extrusion was 314.41% or more. The modified polymer compositions of Examples 1-16 (manufactured using the stabilizer mixture of the present disclosure) are more stable than the modified polymer compositions of Comparative Examples 1-17 and 20-21. There is a clear improvement.

  In particular, samples E1 and E10 prepared from the modified polymer compositions of Examples 1 and 10 (containing organic phosphorus-containing antioxidant A1 and sulfur-containing carboxylates B1 and B2) are comparative examples. Better processing compared to sample CE11 made from 11 modified polymer composition (containing organophosphorus-containing antioxidant A1, but containing sulfur-containing carboxylic acid ester DSTDP rather than sulfur-containing carboxylate) Has stability. Therefore, it is shown that when a sulfur-containing carboxylate is used in combination with an organic phosphorus-containing antioxidant, it is possible to make it difficult to synergistically change the melt index of the modified polymer composition compared to the corresponding sulfur-containing carboxylate. It is. Further, sample E2 prepared from the modified polymer composition of Example 2 (containing organic phosphorus-containing antioxidant A2 and sulfur-containing carboxylate B1), and modified polymer composition of Comparative Example 12 (organic phosphorus-containing antioxidant) The same conclusion can be drawn from the difference in processing stability with the sample CE12 prepared from the agent A2 but containing the sulfur-containing carboxylic acid ester DSTDP instead of the sulfur-containing carboxylate.

  Samples CE18-CE19 made from the modified polymer compositions of Comparative Examples 18-19 (containing PE) and Samples E17-E18 made from the modified polymer compositions of Examples 17-18 (containing PE) Notably, the processing stability of the modified polymer composition produced from PE is described below based on the difference in melt index. In evaluating processing stability, it should be noted that a sample made from PE and a sample made from PP are evaluated separately depending on the difference in properties (crosslinking degree, tendency to crack, etc.). . Specifically, the MI value of a sample made from PP usually increases with the number of extrusions (the ΔMI value increases as the number of extrusions increases), while the MI value of a sample made from PE usually , Decreases as the number of extrusions (the ΔMI value decreases as the number of extrusions increases). Thus, samples made from PP show good processing stability unless the ΔMI value increases significantly with the number of extrusions, while samples made from PE show ΔMI values with the number of extrusions. Show good processing stability.

  In samples E17 to E18 (manufactured by PE), the ΔMI value of the sample after the third extrusion process is 96.06% or more, and the ΔMI value of the sample after the fifth extrusion process is 90.15%. That was all. On the other hand, in samples CE18 to CE19 (manufactured by PE), the ΔMI value of the sample after the third extrusion is 95.11% or less, and the ΔMI value of the sample after the fifth extrusion is 87.11%. It was 33% or less. The modified polymer compositions of Examples 17-18 (produced using the stabilizer mixture of the present disclosure) have clearly improved processing stability compared to the modified polymer compositions of Comparative Examples 18-19. doing.

  In addition to the above processing stability provided by the stabilizer mixture of the present disclosure as indicated by the ΔMI value of Table 3, the ΔMI value of Table 3 is calculated to further demonstrate the effect of the stabilizer mixture of the present disclosure. Table 5 shows the MI values of the samples E1 to E18 prepared from the modified polymer compositions of Examples 1 to 18, which are the numerical values used for the above.

  The low MI values for Samples E1-E16 shown in Table 5 indicate that the stabilizer mixture of the present disclosure can impart good physical properties to polymer compositions made from PP (ie, the lower the MI value, the more PP The higher MI values of samples E17-E18 shown in Table 5 are better for polymer compositions made from PE than the physical properties of polymer compositions made from It shows that physical properties can be imparted (that is, the higher the MI value, the better the physical properties of the polymer composition made from PE). Furthermore, the following comparison between samples made from PP can further illustrate the effect that the stabilizer mixture of the present disclosure has on the physical properties of the polymer composition. CE11 (organophosphorus-containing antioxidant A1 containing an organic phosphorus-containing antioxidant A1 after the first, third, and fifth extrusions, respectively) were 0.3828, 0.6729, and 1.4097, respectively. Sample E1 and E10 (containing organic phosphorus-containing antioxidant A1 and any of sulfur-containing carboxylates B1 and B2) compared to The MI value after processing is lower. Similarly, sample CE12 (containing organic phosphorus-containing antioxidant A2 but containing sulfur containing an organic phosphorus content) having MI values of 0.3616, 0.6534, and 1.1369 after the first, third, and fifth extrusions, respectively. Sample E2 (containing organophosphorus-containing antioxidant A2 and sulfur-containing carboxylate B1) is compared with the sample after several extrusions, compared to sulfur-containing carboxylic acid ester DSTDP rather than carboxylate). The MI value is lower. Thus, the stabilizer mixture of the present disclosure not only provides processing stability of the polymer composition, but also imparts good physical properties to the polymer composition.

  In the description above, for the purposes of explanation, numerous specific details are set forth in order to facilitate an overall understanding of the present disclosure. However, it will be apparent to one skilled in the art that one or more other embodiments may be practiced without the specific details. In addition, in the description indicating “one embodiment” and “one embodiment” in this specification, all the descriptions accompanied by indications such as ordinal numbers are included in the specific implementation of the present disclosure having specific aspects, structures, and features. It should be understood that this is possible. Furthermore, in this description, sometimes multiple variations are incorporated into one embodiment, figure, or description thereof, but this is for the purpose of streamlining the description and is intended to further enhance the versatility of the present invention. It is intended to be understood.

  As mentioned above, although preferable embodiment and the example of a change of this invention were described, this invention is not limited to these, All modifications and equality | equation are as various structures included in the mind and range of the widest interpretation. Including the structure.

Claims (13)

A stabilizer mixture for modification of olefinic polymers,
At least one organic phosphorus represented by the formula selected from the group consisting of formulas (1), (2), (3), (4), (5), (6), (7) and (8) Containing antioxidants,
A stabilizer mixture comprising at least one sulfur-containing carboxylate represented by the formula selected from the group consisting of formulas (9), (10), (11) and (12).
Provided that R ¹¹ , R ¹² , and R ¹³ are independently selected from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and linear C ₁ -C ₈ alkyl group;
Provided that R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ are independently selected from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and linear C ₁ -C ₈ alkyl group. Selected
Provided that R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are independently selected from the group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and linear C ₁ -C ₈ alkyl group;
However,
R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ are a group consisting of hydrogen, tert-butyl group, isopropylphenyl group, and 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,
However,
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , and R ⁵⁶ are independently selected from the group consisting of hydrogen, tert-butyl, isopropylphenyl, and linear C ₁ -C ₈ alkyl. ,and,
Z ⁵¹ is selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups;
However,
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 a C ₁ -C ₁₈ hydrocarbon group, and
Wherein R ⁶⁵ , R ⁶⁶ , and R ⁶⁷ are independently selected from the group consisting of hydrogen, tert-butyl, isopropylphenyl, and straight-chain C ₁ -C ₈ alkyl groups. Selected, and
Z ⁶¹ is selected from the group consisting of O, S, and C ₁ -C ₄ alkylene groups;
Provided that R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are hydrogen, tert-butyl group, isopropylphenyl group, and straight-chain C ₁ -C ₈ alkyl group. Selected independently from the group
However,
R ⁹¹ is selected from the group consisting of hydrogen and a C ₁ -C ₁₈ alkyl group;
R ⁹² is selected from the group consisting of a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group;
M ^{q +} is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ , and Al ³⁺ ,
q is an integer of 2 or 3, and
t is an integer in the range of 0-6,
However,
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 a C ₁ -C ₃₀ alkyl group and a C ₆ -C ₁₈ aryl group, and
a and b are each an integer ranging from 1 to 6,
However,
X ²¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , and Zn ²⁺ ,
G ¹ and G ² are
Wherein c and d are each integers in the range of 1-6, and
p is an integer in the range of 1 to 9, provided that when p is an integer of 2 or greater than 2, a plurality of G ¹ may be the same or different, and a plurality of X ²¹ may be the same or different. Often,
However,
X ³¹ is selected from the group consisting of Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , and Zn ²⁺ , and
Y ³¹ is selected from the group consisting of a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₁₈ aryl group, and a group represented by R ⁹³ OOC— (CH ₂ ) _k —, wherein R ⁹³ is C ₁ -C Selected from the group consisting of ₃₀ alkyl groups and C ₆ -C ₁₈ aryl groups, k is an integer in the range of 1-5. R ⁹¹ represents hydrogen,
The stabilizer mixture of claim 1, wherein R ⁹² is selected from the group consisting of a C ₁ -C ₁₈ alkyl group and a C ₆ -C ₁₈ aryl group. The stabilizer mixture of claim 2, wherein R ⁹² is dodecyl.   The antioxidant according to any one of claims 1 to 3, further comprising an antioxidant selected from the group consisting of a hindered phenol-based antioxidant, a benzofuranone-based antioxidant, an amine oxide-based antioxidant, and combinations thereof. The stabilizer mixture described.   The hindered phenol antioxidant is pentaerythritol-tetra- [β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], ethylene bis (oxyethylene) bis [β- (3 -tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris (butylcresol) butane, 4,4'-butylidenebis (6-tert-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'-methylenebis- (4-methyl-6-tert-butylphenol), oct Tyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 1,2-di [-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazide, 2,2 The stabilizer mixture of claim 4, selected from the group consisting of '-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], and combinations thereof.   The benzofuranone antioxidant includes xylyldibutylbenzofuranone, 5- (tert-butyl) -3- [5- (tert-butyl) -2-hydroxyphenyl] benzofuran-2 (3H) -one, 3- [ Selected from the group consisting of 3,5-bis (1,1-dimethylethyl) -2-hydroxyphenyl] -5,7-bis (1,1-dimethylethyl) -2 (3H) -benzofuranone, and combinations thereof The stabilizer mixture of claim 4.   5. The stabilizer mixture of claim 4, wherein the amine oxide-based antioxidant is selected from the group consisting of bis (hydrogenated tallow alkyl) amine, bis (octadecyl) hydroxylamine, and combinations thereof.   The stabilizer mixture according to any one of claims 1 to 7, further comprising an additive selected from the group consisting of antacids, metal deactivators, and combinations thereof.   The stabilizer mixture of claim 8, wherein the antacid is a fatty acid salt.   9. The stabilizer mixture of claim 8, wherein the metal deactivator is oxalyl-bis (benzylidene) hydrazide. An olefin polymer selected from the group consisting of polyolefin, ethylene-vinyl acetate copolymer, and combinations thereof;
A modified polymer composition comprising the stabilizer mixture according to any one of claims 1 to 10.   The modified polymer composition of claim 11, wherein the stabilizer mixture is present in an amount ranging from 0.01 to 2.2 parts by weight with respect to 100 parts by weight of the olefinic polymer.   The modified polymer composition according to claim 11 or 12, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, and combinations thereof.