CN116355303A - A kind of polymer material composition and its application in ES fiber - Google Patents

Abstract

The invention provides a polymer material composition and its application in ES fiber. The polymer material composition includes high-density polyethylene and an antioxidant composition, and the antioxidant composition includes: a hindered amine light stabilizer, a phosphite antioxidant and an acid scavenger. The polymer material composition of the present invention has excellent resistance to gas fumigation (NO _x ) fading, and low yellowness index, and can be used as a cortex material in ES fibers to keep ES fibers in good condition during storage and use. appearance color.

Description

A polymer material composition and its application in ES fiber

Technical Field

The invention relates to the field of polymer material functional additives, and in particular to a polymer material composition and application thereof in ES fibers.

Background Art

ES (Ethylene-Propylene Side By Side) composite fiber is a heat-bonded fiber developed by Chisso Corporation of Japan. This fiber is a two-component skin-core composite fiber. The skin layer has a low melting point and good softness, while the core layer has a high melting point and high strength. After heat treatment, part of the skin layer melts to play a bonding role, while the rest remains in the fiber state. ES fiber is a clean fiber that does not use adhesives, so it is widely used in sanitary materials such as diapers.

There are two main types of ES fibers, one is PE (polyethylene) / PP (polypropylene) composite fiber, and the other is PE (polyethylene) / PET (polyethylene terephthalate) composite fiber. PE has become an ideal skin material for ES fibers because of its low melting point and easy processing. According to the processing characteristics of ES composite fibers, the skin layer generally uses HDPE (high-density polyethylene) with a larger melt flow rate.

At present, the antioxidants of HDPE special materials for ES composite fibers are mainly composed of hindered phenols, phosphites and acid absorbers. Such formulations can usually provide good processing stability and certain thermal oxygen stability. However, due to the use of hindered phenol antioxidants, the material does not have sufficient resistance to gas fumigation (NO _X ) fading. In addition, ES fibers are prone to yellowing or reddening during storage and use, which seriously affects the appearance.

Summary of the invention

In order to solve the above technical problems existing in the prior art, the present invention provides a polymer material composition, which can have excellent anti-gas (NO _X ) fading properties by adding a specific antioxidant composition, reduce the yellow index of high-density polyethylene resin, and be applied to ES fiber as a skin material, so that the ES fiber can maintain a good appearance color during storage, use, etc.

To achieve the above object, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a polymer material composition, comprising high-density polyethylene and an antioxidant composition, wherein the antioxidant composition comprises: a hindered amine light stabilizer, a phosphite antioxidant and an acid scavenger.

Compared with the hindered phenol antioxidants commonly used in the prior art, the present invention uses hindered amine light stabilizers as antioxidants, which can make the polyethylene resin material have extremely excellent anti-gas fading properties, avoid the problem of yellowing or reddening of the material surface during long-term storage or use, and make the polyolefin resin have good initial color. The effect is more prominent when it is used for high-density polyethylene (HDPE) with a density of 0.935 to 0.965 g/ ^cm3 .

The phosphite antioxidant in the present invention can make high-density polyethylene and ES fiber have better stability and better initial color during the processing. Since acidic catalysts are often used in the polymerization reaction of polyethylene, the addition of an acid scavenger can remove acidic catalyst residues and avoid the problem of yellowing of the material. The composition of the present application avoids the influence of phenol yellowing on the appearance of the material, ensures the long-term stability of the color of the high-density polyethylene material; at the same time, it can effectively avoid the nitrogen oxide fumigation yellowing problem encountered by hindered phenol antioxidants.

The amount of the hindered amine light stabilizer in the present invention needs to be controlled within an appropriate range. Too little addition is not conducive to the long-term stability of the material. Since ES fiber materials generally have a short service life, the amount of hindered amine light stabilizer added should not be too much, otherwise it will cause waste of resources and increase costs.

In the antioxidant composition of the present invention, based on the total weight of the antioxidant composition, the weight percentage of the hindered amine light stabilizer is 10%-30%, for example, it can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30% and any value therebetween. Preferably, the weight percentage of the hindered amine light stabilizer is 15%-25%.

In the antioxidant composition of the present invention, based on the total weight of the antioxidant composition, the weight percentage of the phosphite antioxidant is 40%-65%, for example, it can be 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% and any value therebetween. Preferably, the weight percentage of the phosphite antioxidant is 45%-55%.

In the antioxidant composition of the present invention, the weight percentage of the acid scavenger is 20%-40% based on the total weight of the antioxidant composition, for example, it can be 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40% and any value therebetween. Preferably, the weight percentage of the acid scavenger is 25%-35%.

According to some embodiments of the present invention, the antioxidant composition includes, by weight percentage: 10%-30% of hindered amine light stabilizer, 40%-65% of phosphite antioxidant, and 20%-40% of acid scavenger.

According to a preferred embodiment of the present invention, the antioxidant composition comprises, by weight percentage: 15%-25% of hindered amine light stabilizer, 45%-55% of phosphite antioxidant and 25%-35% of acid scavenger.

According to some embodiments of the present invention, in the antioxidant composition, the mass ratio of the hindered amine light stabilizer to the phosphite antioxidant is 1:(1.5-6.5), such as 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, 1:6.5 or any value therebetween. Preferably, the mass ratio of the hindered amine light stabilizer to the phosphite antioxidant is 1:(1.8-4.0).

According to some embodiments of the present invention, the hindered amine light stabilizer is selected from non-liquid hindered amine light stabilizers. In a specific implementation, the non-liquid hindered amine light stabilizer is in the form of powder, granules, paste, or masterbatch.

According to a preferred embodiment of the present invention, the hindered amine light stabilizer is selected from ester-linked piperidine series hindered amine light stabilizers and triazine hindered amine light stabilizers; the ester-linked piperidine series hindered amine light stabilizer contains a group shown in formula I, and the triazine hindered amine light stabilizer contains a group shown in formula II:

Wherein, in Formula I and Formula II, R ₁ and R ₂ are each independently selected from H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 ester, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, and the substituted substituent is selected from C1-C5 alkyl, C1-C5 alkoxy, C1-C5 cycloalkyl or C6-C15 aryl;

More preferably, the triazine hindered amine light stabilizer includes a hexamethylenediaminepiperidine series of triazine hindered amine light stabilizers and a butylaminepiperidine series of triazine hindered amine light stabilizers; the hexamethylenediaminepiperidine series of triazine hindered amine light stabilizers further contain a group shown in formula III, and the butylaminepiperidine series of triazine hindered amine light stabilizers further contain a group shown in formula IV,

Wherein, in Formula III and Formula IV, _R1 is selected from H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 ester, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, and the substituted substituent is selected from C1-C5 alkyl, C1-C5 alkoxy, C1-C5 cycloalkyl or C6-C15 aryl.

In some embodiments, the ester-linked piperidine series hindered amine light stabilizer refers to a hindered amine light stabilizer having a structural group of formula I, and the ester-linked piperidine series hindered amine light stabilizer includes but is not limited to bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (i.e., light stabilizer 770), poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol) succinate (i.e., light stabilizer 622), and the like.

In some embodiments, the triazine hindered amine light stabilizer of the hexamethylenediamine piperidine series refers to a hindered amine light stabilizer having a structural group of formula III, and the hexamethylenediamine piperidine series hindered amine light stabilizer includes but is not limited to poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexamethylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]} (i.e., light stabilizer 944), N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and 2,4,6-trichloro -1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine reaction product polymer (i.e., light stabilizer 2020), poly[(6-morpholinyl-1,3,5-triazine-2,4-yl)-((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexane-((2,2,6,6-tetramethyl-4-piperidinyl)imino)] (i.e., light stabilizer 3346), N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine methylated polymer with morpholinyl-2,4,6-trichloro-1,3,5-triazine (i.e., light stabilizer 3529).

In some embodiments, the triazine hindered amine light stabilizer of the butylamine piperidine series refers to a hindered amine light stabilizer having a structural group of formula IV, and the hindered amine light stabilizer of the butylamine piperidine series includes but is not limited to 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-6-yl]-1,5,8,12-tetraazadodecane (i.e., light stabilizer 119), N,N″-1,2-dimethylene-1,3-propylenediamine polymer and the reactant of 2,4,6-trichloro-1,3,5-triazine and N-butyl-2,2,6,6-tetramethyl-4-ammonium (i.e., light stabilizer HA-88), etc.

Wherein, in Formula III and Formula IV, _R1 is selected from H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 ester, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, and the substituted substituent is selected from C1-C5 alkyl, C1-C5 alkoxy, C1-C5 cycloalkyl or C6-C15 aryl.

In some preferred embodiments, R ₁ is selected from H, C1-C10 alkyl, C1-C10 ester, C6-C20 aryl, C7-C20 aralkyl, C1-C10 alkoxy, C6-C20 aryloxy or C7-C20 alkylaryloxy.

In some preferred embodiments, R ₁ is selected from H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, methoxy, ethoxy, phenoxy, alkylphenoxy or dibasic acid ester.

According to some embodiments of the present invention, the hindered amine light stabilizer is selected from a high molecular weight hindered amine light stabilizer. The high molecular weight hindered amine light stabilizer can be a polymeric high molecular weight hindered amine light stabilizer or a non-polymeric high molecular weight hindered amine light stabilizer. Preferably, the molecular weight of the high molecular weight hindered amine light stabilizer is 1000-5000, preferably 2000-4000.

According to some preferred embodiments of the present invention, the hindered amine light stabilizer is selected from at least one of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (i.e., light stabilizer 770), poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol) succinate (i.e., light stabilizer 622) and 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-6-yl]-1,5,8,12-tetraazadodecane (i.e., light stabilizer 119).

According to some embodiments of the present invention, the phosphite antioxidant is selected from phosphite antioxidants having a 2,4-di-tert-butylbenzene structure or a pentaerythritol structure.

According to some preferred embodiments of the present invention, the phosphite antioxidant is selected from at least one of tris(2,4-di-tert-butylphenyl) phosphite (i.e., antioxidant 168), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (i.e., antioxidant 626), and dioctadecyl pentaerythritol diphosphite (i.e., antioxidant 618). In some more preferred embodiments, the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite.

According to some embodiments of the invention, the acid scavenger is a metal stearate.

According to some preferred embodiments of the present invention, the acid scavenger is selected from at least one of zinc stearate, calcium stearate and magnesium stearate. In some more preferred embodiments, the acid scavenger is calcium stearate.

According to some embodiments of the present invention, the antioxidant composition includes light stabilizer 622, antioxidant 168 and calcium stearate.

According to some embodiments of the invention, the antioxidant composition includes, by weight percentage, 15-25% of light stabilizer 622 (e.g., 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%), and/or 45-55% of antioxidant 168 (e.g., 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%), and/or 25-35% of calcium stearate (e.g., 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%).

According to some embodiments of the present invention, the melt flow rate MFR of the high density polyethylene is 10-40 g/10 min, such as 10 g/10 min, 15 g/10 min, 20 g/10 min, 25 g/10 min, 30 g/10 min, 35 g/10 min, 40 g/10 min or any value therebetween, preferably 15-25 g/10 min.

According to some embodiments of the present invention, based on the mass of the high-density polyethylene, the added amount of the antioxidant composition is 1300-2500ppm, for example, it can be 1300ppm, 1500ppm, 1700ppm, 1900ppm, 2100ppm, 2300ppm, 2500ppm or any value therebetween, preferably 1500-2000ppm.

According to some embodiments of the present invention, the antioxidant composition is added to the high-density polyethylene in an amount of 0.13%-0.25%, preferably 0.15%-0.2%.

In a second aspect, the present invention provides an ES fiber cortex material, comprising the polymer material composition described in the first aspect of the present invention.

In a third aspect, the present invention provides an ES fiber, comprising a skin layer and a core layer, wherein the skin layer comprises the polymer material composition described in the first aspect of the present invention.

In the present invention, the core layer of the ES fiber may be polypropylene (PP) or polyethylene terephthalate (PET) or a mixture of both.

In a fourth aspect, the present invention provides the use of the polymer material composition described in the first aspect in ES fibers, preferably in the production, processing, use, storage and transportation of ES fibers.

The beneficial effects of the present invention are as follows: the antioxidant composition of the present invention uses a hindered amine light stabilizer as an antioxidant, and is used in combination with a phosphite antioxidant and an acid scavenger, and the amount of the antioxidant composition added to polyethylene is optimized, so that the polyethylene resin has good processing stabilizer, heat-oxidative aging resistance and excellent anti-gas fading performance, and is used in ES fiber to enable the ES fiber to maintain a good appearance color and high stability.

DETAILED DESCRIPTION

In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation of the present invention. The actual protection scope of the present invention is set forth in the claims. It should be understood that any modifications and changes can be made without departing from the spirit of the present invention.

The ES (Ethylene-Propylene Side By Side) fiber of the present invention is a two-component composite fiber with a core-skin structure. The skin material is usually a resin material with a low melting point and good softness, such as polyolefin, and the core material is usually a resin with a high melting point and high strength, such as polypropylene, polyethylene terephthalate, etc. After heat treatment, a part of the skin layer of the fiber melts to play a bonding role, and the rest remains in a fiber state. At the same time, it has the characteristic of a small heat shrinkage rate and is suitable for use as a hot air penetration process to produce sanitary materials, thermal insulation filling materials, filter materials and other products.

Unless otherwise specified, the reagents used in the following examples of the present invention were obtained from commercial sources.

The hindered amine light stabilizer 770 used in the following examples is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, CAS No.: [52829-07-9].

Hindered amine light stabilizer 622 is poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol) succinate, CAS No.: [65447-77-0].

Hindered amine light stabilizer 944 is poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidinyl)-imino]}, CAS No.: [70624-18-9; 71878-19-8].

The hindered amine light stabilizer 119 is 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-6-yl]-1,5,8,12-tetraazadodecane, CAS No.: [106990-43-6].

Hindered amine light stabilizer 2020 is a polymer of the reaction product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, CAS No.: [192268-64-7].

The hindered phenol antioxidant 1010 used in the following comparative examples is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, CAS No.: [6683-19-8].

Hindered phenol antioxidant 3114 is 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, CAS No.: [27676-62-6].

Example 1

(1) Preparation of antioxidant composition

Based on the total weight of the composition, 17.65% of the light stabilizer 622, 52.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) prepared by the Hostalen ACP process and having a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 2

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65% of the light stabilizer 770, 52.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 3

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65% of the light stabilizer 944, 52.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 4

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65% of light stabilizer 2020, 52.94% of antioxidant 168, and 29.41% of calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 5

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65 wt % of light stabilizer 119, 52.94 wt % of antioxidant 168, and 29.41 wt % of calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 6

(1) Preparation of antioxidant composition

Based on the total weight of the composition, 25% of the light stabilizer 622, 45% of the antioxidant 168, and 30% of the calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) prepared by the Hostalen ACP process and having a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 7

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 10% of the light stabilizer 770, 65% of the antioxidant 168, and 25% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 8

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65 wt % of light stabilizer 119, 52.94 wt % of antioxidant 618, and 29.41 wt % of calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 9

(1) Preparation of antioxidant composition

Based on the total weight of the composition, 7.65% of the light stabilizer 622, 62.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) prepared by the Hostalen ACP process and having a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Example 10

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 57.65% of the light stabilizer 944, 12.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

The components and weight percentages of the antioxidant compositions in Examples 1-10 and Comparative Examples 1-3, as well as the amounts of the antioxidant compositions added to HDPE are listed in Table 1.

Comparative Example 1

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 23.46% of the hindered phenol antioxidant 1010, 46.92% of the antioxidant 168, and 29.62% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1300 ppm of the antioxidant composition of step (1) is added for blending and mixing, and HDPE composition particles are obtained by an extrusion granulator at a temperature of 210° C.

Comparative Example 2

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 17.65% of the hindered phenol antioxidant 3114, 52.94% of the antioxidant 168, and 29.41% of the calcium stearate are mixed to obtain the antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 1700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Comparative Example 3

(1) Preparation of antioxidant composition

Based on the total weight of the antioxidant composition, 3.7% of hindered phenol antioxidant 1010, 66.67% of antioxidant 168, 11.11% of 626, and 18.52% of calcium stearate are mixed to obtain an antioxidant composition.

(2) Preparation of HDPE composition

HDPE (powder) with a melt index of 20 g/10 min at 190° C. under a load of 2.16 kg prepared by the Hostalen ACP process is used as a matrix, 2700 ppm of the antioxidant composition of step (1) is added for blending, and HDPE composition particles are obtained by an extrusion granulator at an extruder temperature of 210° C.

Table 1

Performance test (I):

The initial YI of the HDPE granules after granulation, the YI of the injection molded samples and the yellowness index after the fumigation test in Examples 1-10 and Comparative Examples 1-3 were tested, and the results are shown in Table 2. Among them, the YI was tested according to ASTM E313-2005; the fumigation test was carried out according to the method of JIS L-0855. In order to shorten the test time, the sample concentration was twice that of the standard, and the sample thickness was 1 mm.

Table 2 Initial YI of HDPE granules after granulation, YI of injection molded samples and yellow index after fumigation test

As can be seen from Table 2, compared with comparative examples 1-3 using hindered phenol antioxidants as antioxidants, in Examples 1 to 10 of the present application, hindered amine light stabilizers are used as antioxidants, and the obtained high-density polyethylene resins not only have lower initial YI values for the samples, but also have lower YI change values after 3 days and 6 days of fumigation, indicating that the use of a specific antioxidant composition in the present invention can make the polyethylene material have a lower initial color and better resistance to fumigation fading.

Performance test (II):

The YI of the injection molded samples in Examples 1-10 and Comparative Examples 1-3 and the YI after heat aging (tested in accordance with ASTM E313-2005) and the tensile properties (tested in accordance with GB/T1040.2-2006) were tested, and the results are shown in Table 3. The heat aging test was carried out at 100°C, the YI was tested in accordance with ASTM E313-2005, and the tensile properties were tested in accordance with GB/T1040.2-2006.

Table 3 MFR after granulation, YI of injection molded samples, YI after heat aging, and tensile properties

As can be seen from Table 3, after thermal aging, the change in YI of the polyethylene materials in Examples 1-10 is small. The compositions in the examples do not contain hindered phenol antioxidants, which avoids the effect of phenol yellowing on the appearance of the material and ensures the long-term stability of the color of the high-density polyethylene material; at the same time, it can effectively avoid the nitrogen oxide fumigation yellowing problem encountered by hindered phenol antioxidants. Especially in Example 1, Example 2, Example 5, Example 6, and Example 8, the change in YI after thermal aging is much lower than that of the corresponding comparative example. Light stabilizer 944 and light stabilizer 2020 in Example 3 and Example 4 are both triazine hindered amine light stabilizers belonging to the hexamethylenediaminepiperidine series, and the thermal aging ΔYI is slightly higher, which may be related to the structure of this type of hindered amine.

In summary, from the comprehensive view of the indicators such as polyethylene resin granulation YI, sample initial YI, yellow index after fumigation and yellow index after heat aging, the polyethylene resin materials prepared in Examples 1, 2, 5, 6 and 8 have better performance.

Although the present invention has been described in detail above by general description, specific implementation methods and experiments, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, these modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims (10)

1. A polymeric material composition comprising a high density polyethylene and an antioxidant composition, the antioxidant composition comprising: hindered amine light stabilizer, phosphite antioxidant and acid scavenger.

2. The polymer material composition according to claim 1, wherein the antioxidant composition comprises, in weight percent, 10% -30% of hindered amine light stabilizer, 40% -65% of phosphite antioxidant and 20% -40% of acid scavenger;

preferably, the antioxidant composition comprises, by weight, 15% -25% of hindered amine light stabilizer, 45% -55% of phosphite antioxidant and 25% -35% of acid scavenger.

3. The polymeric material composition according to claim 1 or 2, wherein the hindered amine light stabilizer is selected from non-liquid hindered amine light stabilizers;

preferably, the hindered amine light stabilizer is selected from the group consisting of ester-linked piperidine series hindered amine light stabilizers and triazine-based hindered amine light stabilizers; the ester-linked piperidine series hindered amine light stabilizer comprises a group shown in a formula I, and the triazine series hindered amine light stabilizer comprises a group shown in a formula II;

wherein in formula I and formula II, R ₁ 、R ₂ Each independently selected from H,A substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 ester group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C6-C20 aryloxy group, said substituted substituent being selected from the group consisting of C1-C5 alkyl group, C1-C5 alkoxy group, C1-C5 cycloalkyl group, and C6-C15 aryl group;

more preferably, the triazine hindered amine light stabilizer comprises a triazine hindered amine light stabilizer of hexamethylenediamine piperidine series, a triazine hindered amine light stabilizer of butylaminpiperidine series; the triazine hindered amine light stabilizer of the hexamethylenediamine piperidine series also contains a group shown in a formula III, the hindered amine light stabilizer of the butylamine piperidine series triazine also contains a group shown in a formula IV,

wherein in formula III and formula IV, R ₁ Selected from H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 ester, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C20 aryloxy, said substituted substituent being selected from C1-C5 alkyl, C1-C5 alkoxy, C1-C5 cycloalkyl or C6-C15 aryl.

4. A polymeric material composition according to claim 3, wherein the ester-linked piperidine series of hindered amine light stabilizers is selected from at least one of bis (2, 6-tetramethyl-4-piperidinyl) sebacate, poly (4-hydroxy-2, 6-tetramethyl-1-piperidylethanol) ester;

the triazine hindered amine light stabilizer of the hexamethylenediamine piperidine series is selected from poly- { [6- [ (1, 3-tetramethylbutyl) -imino ] -1,3, 5-triazin-2, 4-diyl ] [2- (2, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2, 6-tetramethylpiperidinyl) -imino ] }, N is a number of the N, polymers of the reaction product of N '-bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexanediamine with 2,4, 6-trichloro-1, 3, 5-triazine and N-butyl-1-butylamine and N-butyl-2, 6-tetramethyl-4-piperidinamine poly [ (6-morpholino-1, 3, 5-triazin-2, 4-yl) - ((2, 6-tetramethyl-4-piperidinyl) imino) hexane- ((2, 6-tetramethyl-4-piperidinyl) imino) ], N, at least one of the methylated polymers of N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and morpholine-2, 4, 6-trichloro-1, 3, 5-triazine;

the triazine hindered amine light stabilizer of the butylamine piperidine series is selected from 1,5,8, 12-tetra [2, 4-bis (N-butyl-N-1, 2, 6-pentamethyl-4-piperidylamino) -1,3, 5-triazin-6-yl ] -1,5,8, 12-tetraazadodecane and N, at least one of reactants of N' -1, 2-dimethylene-1, 3-propanediamine polymer and 2,4, 6-trichloro-1, 3, 5-triazine and N-butyl-2, 6-tetramethyl-4-ammonium.

5. The polymer composition according to any one of claims 1 to 4, wherein the phosphite antioxidant is selected from phosphite antioxidants having a structure of 2, 4-di-t-butylbenzene or pentaerythritol;

preferably, the phosphite antioxidant is at least one selected from tri (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and pentaerythritol diphosphite;

and/or the acid scavenger is a metal stearate; preferably, the acid scavenger is selected from at least one of zinc stearate, calcium stearate and magnesium stearate.

6. The polymeric material composition of any one of claims 1-5, wherein the antioxidant composition comprises poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, tris (2, 4-di-t-butylphenyl) phosphite and calcium stearate;

preferably, the antioxidant composition comprises, in weight percent, 15-25% poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 45-55% tris (2, 4-di-tert-butylphenyl) phosphite and 25-35% calcium stearate.

7. The polymeric material composition according to any one of claims 1 to 6, wherein the high density polyethylene has a melt flow rate MFR of 10-40g/10min, preferably 15-25g/10min.

8. An ES fiber sheath material comprising the polymeric material composition of any one of claims 1-7.

9. An ES fiber comprising a sheath layer and a core layer, the sheath layer comprising the polymeric material composition of any one of claims 1-7.

10. Use of the polymeric material composition of any one of claims 1-7 in ES fiber production, processing, use, storage, transportation.