A polymeric material composition and its application in ES fibers

Abstract

This invention provides a polymeric material composition and its application in ES fibers. The polymeric material composition comprises high-density polyethylene and an antioxidant composition, wherein the antioxidant composition comprises: a hindered amine light stabilizer, a phosphite antioxidant, and an acid scavenger. The polymeric material composition of this invention exhibits excellent resistance to NO₂ (NO₃) fumes. X Its low fading and yellow index make it suitable as a sheath material in ES fibers, allowing ES fibers to maintain a good appearance and color during storage and use.

Description

Technical Field

[0001] This invention relates to the field of functional additives for polymer materials, and more specifically to a polymer material composition and its application in ES fibers. Background Technology

[0002] 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 core-sheath composite fiber; the sheath 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 sheath layer melts to act as a binder, while the rest retains its fibrous state. ES fiber is a clean fiber that does not use adhesives, so it is widely used in hygiene materials such as diapers.

[0003] 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, due to its lower melting point and ease of processing, has become the ideal sheath material for ES fibers. Based on the processing characteristics of ES composite fibers, the sheath is generally made of HDPE (high-density polyethylene), which has a higher melt flow rate.

[0004] Currently, the antioxidants in HDPE-specific materials for ES composite fibers mainly consist of hindered phenols, phosphites, and acid scavengers. These formulations typically provide good processing stability and a certain degree of thermo-oxidative stability. However, due to the use of hindered phenolic antioxidants, the material does not possess sufficient resistance to NO₂ (NO₃) fumes. X ) Fading. In addition, ES fibers are prone to yellowing or reddening during storage and use, which seriously affects their appearance. Summary of the Invention

[0005] To address the aforementioned technical problems in the prior art, this invention provides a polymer material composition that, by incorporating a specific antioxidant composition, exhibits excellent resistance to NO₂ (NO₃) fumes. X It reduces fading and lowers the yellow index of high-density polyethylene resin. When used as a skin material in ES fibers, it can help ES fibers maintain a good appearance color during storage and use.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a polymeric 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 remover.

[0008] Compared to hindered phenolic antioxidants commonly used in existing technologies, this invention uses hindered amine light stabilizers as antioxidants, which enables polyethylene resin materials to exhibit extremely excellent resistance to fading from fumes. This prevents the material surface from yellowing or reddening during long-term storage or use, and maintains the good initial color of the polyolefin resin, especially for materials with densities of 0.935–0.965 g / cm³. 3 The effect is more pronounced when using high-density polyethylene (HDPE).

[0009] The phosphite antioxidant in this invention enables high-density polyethylene and ES fibers to exhibit good stability and initial color during processing. Since acidic catalysts are commonly used in the polymerization reaction of polyethylene, the addition of an acid-removing agent can remove acidic catalyst residues and prevent the material from yellowing. The composition of this application avoids the impact of phenolic yellowing on the material's appearance, ensuring the long-term color stability of the high-density polyethylene material; simultaneously, it effectively avoids the yellowing problem caused by nitrogen oxide gas exposure to hindered phenolic antioxidants.

[0010] The amount of hindered amine light stabilizer used in this invention needs to be controlled within a suitable range; too little addition is detrimental to the long-term stability of the material. Since ES fiber materials generally have a relatively short service life, the amount of hindered amine light stabilizer added should also not be excessive, otherwise it will lead to resource waste and increased costs.

[0011] In the antioxidant composition of the present invention, the hindered amine light stabilizer has a weight percentage of 10%-30% based on the total weight of the antioxidant composition, for example, it can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, and any value between therewith. Preferably, the hindered amine light stabilizer has a weight percentage of 15%-25%.

[0012] 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 between therewith. Preferably, the weight percentage of the phosphite antioxidant is 45%-55%.

[0013] In the antioxidant composition of the present invention, the weight percentage of the scavenging agent 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 between therewith. Preferably, the weight percentage of the scavenging agent is 25%-35%.

[0014] According to some embodiments of the present invention, the antioxidant composition comprises, by weight percentage: 10%-30% hindered amine light stabilizer, 40%-65% phosphite antioxidant, and 20%-40% acid remover.

[0015] According to a preferred embodiment of the present invention, the antioxidant composition comprises, by weight percentage: 15%-25% hindered amine light stabilizer, 45%-55% phosphite antioxidant, and 25%-35% acid remover.

[0016] 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), for example 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 between them. Preferably, the mass ratio of the hindered amine light stabilizer to the phosphite antioxidant is 1:(1.8-4.0).

[0017] According to some embodiments of the present invention, the hindered amine light stabilizer is selected from non-liquid hindered amine light stabilizers. In specific implementations, the non-liquid hindered amine light stabilizer is in the form of powder, granules, paste, or masterbatch.

[0018] 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 represented by Formula I, and the triazine hindered amine light stabilizer contains a group represented by Formula II.

[0019]

[0020] In Formula I and Formula II, R1 and R2 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;

[0021] More preferably, the triazine-based hindered amine light stabilizer includes hexamethylenediamine piperidine series triazine-based hindered amine light stabilizers and butylamine piperidine series triazine-based hindered amine light stabilizers; the hexamethylenediamine piperidine series triazine-based hindered amine light stabilizers further contain the group shown in Formula III, and the butylamine piperidine series triazine-based hindered amine light stabilizers further contain the group shown in Formula IV.

[0022]

[0023] In Formulas III and 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.

[0024] 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. The ester-linked piperidine series hindered amine light stabilizers include, but are not limited to, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (i.e., light stabilizer 770) and poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester (i.e., light stabilizer 622).

[0025] In some embodiments, the hexamethylenediamine piperidine series of triazine hindered amine light stabilizers refers to hindered amine light stabilizers having a structural group of formula III. These hexamethylenediamine piperidine series hindered amine light stabilizers include, but are 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]-hexylene-[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 Polymers of the reaction products of -1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine (i.e., light stabilizer 2020), poly[(6-morpholino-1,3,5-triazine-2,4-yl)-((2,2,6,6-tetramethyl-4-piperidinyl)imine)hexane-((2,2,6,6-tetramethyl-4-piperidinyl)imine)] (i.e., light stabilizer 3346), and methylated polymers of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with morpholino-2,4,6-trichloro-1,3,5-triazine (i.e., light stabilizer 3529).

[0026] In some embodiments, the hindered amine light stabilizers of the butylamine-piperidine series triazine class refer to hindered amine light stabilizers having a structural group of formula IV. The hindered amine light stabilizers of the butylamine-piperidine series include, but are not limited to, 1,5,8,12-tetra[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), the reaction product of N,N”-1,2-dimethylene-1,3-propanediamine polymer with 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.

[0027]

[0028] In Formulas III and 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.

[0029] In some preferred embodiments, R1 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.

[0030] In some preferred embodiments, R1 is selected from H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, methoxy, ethoxy, phenoxy, alkylphenoxy, or diester group.

[0031] According to some embodiments of the present invention, the hindered amine light stabilizer is selected from high molecular weight hindered amine light stabilizers. 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, more preferably 2000-4000.

[0032] 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-piperidinylethanol) ester (i.e., light stabilizer 622), and 1,5,8,12-tetra[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-6-yl]-1,5,8,12-tetraazadodecane (i.e., light stabilizer 119).

[0033] 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.

[0034] 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), pentaerythritol diphosphite (i.e., antioxidant 626), and pentaerythritol dioctadecaphosphite (i.e., antioxidant 618). In some more preferred embodiments, the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite.

[0035] According to some embodiments of the present invention, the deacidifying agent is a metal stearate salt.

[0036] According to some preferred embodiments of the present invention, the deacidifying agent is selected from at least one of zinc stearate, calcium stearate, and magnesium stearate. In some more preferred embodiments, the deacidifying agent is calcium stearate.

[0037] According to some embodiments of the present invention, the antioxidant composition includes light stabilizer 622, antioxidant 168, and calcium stearate.

[0038] According to some embodiments of the present invention, the antioxidant composition comprises, 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%).

[0039] According to some embodiments of the present invention, the melt flow rate (MFR) of the high-density polyethylene is 10-40 g / 10 min, for example 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 between them. Preferably, it is 15-25 g / 10 min.

[0040] According to some embodiments of the present invention, based on the mass of the high-density polyethylene, the amount of the antioxidant composition added is 1300-2500 ppm, for example, it can be 1300 ppm, 1500 ppm, 1700 ppm, 1900 ppm, 2100 ppm, 2300 ppm, 2500 ppm or any value between them, preferably 1500-2000 ppm.

[0041] According to some embodiments of the present invention, the amount of the antioxidant composition added to the high-density polyethylene is 0.13-0.25%, preferably 0.15%-0.2%.

[0042] In a second aspect, the present invention provides an ES fiber skin material comprising the polymeric material composition described in the first aspect of the present invention.

[0043] Thirdly, the present invention provides an ES fiber comprising a sheath and a core, wherein the sheath comprises the polymeric material composition described in the first aspect of the present invention.

[0044] In this invention, the core layer of the ES fiber can be one or a mixture of two of polypropylene (PP) or polyethylene terephthalate (PET).

[0045] Fourthly, the present invention provides the application of the polymeric material composition described in the first aspect in ES fibers, preferably in the production, processing, use, storage and transportation of ES fibers.

[0046] The beneficial effects of the present invention are as follows: The antioxidant composition of the present invention uses hindered amine light stabilizer as antioxidant, and by using it in combination with phosphite antioxidant and deacidifying agent, and by optimizing the amount of antioxidant composition added to polyethylene, the polyethylene resin has good processing stabilizer, anti-thermal and oxidative aging performance and excellent anti-fading property. When used in ES fiber, it can enable ES fiber to maintain good appearance color and high stability. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. The actual scope of protection of this 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 this invention.

[0048] The ES (Ethylene-Propylene Side By Side) fiber described in this invention is a bicomponent core-sheath composite fiber. The sheath material is typically a resin material with a low melting point and good flexibility, such as polyolefin, while the core material is typically a resin with a high melting point and high strength, such as polypropylene or polyethylene terephthalate. After heat treatment, part of the fiber's sheath melts and acts as a binder, while the remainder retains its fibrous state. It also features low thermal shrinkage, making it suitable for use in the production of sanitary materials, thermal insulation fillers, and filter materials using hot air penetration processes.

[0049] Unless otherwise specified, all reagents used in the following embodiments of the present invention are commercially available.

[0050] 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].

[0051] Hindered amine light stabilizer 622 is polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, CAS No.: [65447-77-0].

[0052] 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].

[0053] Hindered amine light stabilizer 119 is 1,5,8,12-tetra[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-6-yl]-1,5,8,12-tetraazadodecane, CAS No.: [106990-43-6].

[0054] Hindered amine light stabilizer 2020 is a polymer of the reaction products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with 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].

[0055] The hindered phenolic 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].

[0056] The hindered phenolic 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].

[0057] Example 1

[0058] (1) Preparation of antioxidant composition

[0059] Based on the total weight of the composition, 17.65% of light stabilizer 622, 52.94% of antioxidant 168, and 29.41% of calcium stearate are mixed to obtain an antioxidant composition.

[0060] (2) Preparation of HDPE composition

[0061] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0062] Example 2

[0063] (1) Preparation of antioxidant composition

[0064] The antioxidant composition is obtained by mixing light stabilizer 770 (17.65%), antioxidant 168 (52.94%), and calcium stearate (29.41%) based on the total weight of the antioxidant composition.

[0065] (2) Preparation of HDPE composition

[0066] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0067] Example 3

[0068] (1) Preparation of antioxidant composition

[0069] The antioxidant composition is obtained by mixing 17.65% light stabilizer 944, 52.94% antioxidant 168, and 29.41% calcium stearate based on the total weight of the antioxidant composition.

[0070] (2) Preparation of HDPE composition

[0071] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0072] Example 4

[0073] (1) Preparation of antioxidant composition

[0074] 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 were mixed to obtain the antioxidant composition.

[0075] (2) Preparation of HDPE composition

[0076] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0077] Example 5

[0078] (1) Preparation of antioxidant composition

[0079] Based on the total weight of the antioxidant composition, 17.65% by weight of light stabilizer 119, 52.94% by weight of antioxidant 168, and 29.41% by weight of calcium stearate are mixed to obtain the antioxidant composition.

[0080] (2) Preparation of HDPE composition

[0081] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0082] Example 6

[0083] (1) Preparation of antioxidant composition

[0084] Based on the total weight of the composition, 25% of light stabilizer 622, 45% of antioxidant 168, and 30% of calcium stearate are mixed to obtain an antioxidant composition.

[0085] (2) Preparation of HDPE composition

[0086] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0087] Example 7

[0088] (1) Preparation of antioxidant composition

[0089] Based on the total weight of the antioxidant composition, 10% of light stabilizer 770, 65% of antioxidant 168, and 25% of calcium stearate are mixed to obtain the antioxidant composition.

[0090] (2) Preparation of HDPE composition

[0091] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0092] Example 8

[0093] (1) Preparation of antioxidant composition

[0094] The antioxidant composition is obtained by mixing light stabilizer 119 (17.65% by weight), antioxidant 618 (52.94% by weight), and calcium stearate (29.41% by weight) based on the total weight of the antioxidant composition.

[0095] (2) Preparation of HDPE composition

[0096] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0097] Example 9

[0098] (1) Preparation of antioxidant composition

[0099] Based on the total weight of the composition, 7.65% of light stabilizer 622, 62.94% of antioxidant 168, and 29.41% of calcium stearate are mixed to obtain an antioxidant composition.

[0100] (2) Preparation of HDPE composition

[0101] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0102] Example 10

[0103] (1) Preparation of antioxidant composition

[0104] The antioxidant composition is obtained by mixing 57.65% light stabilizer 944, 12.94% antioxidant 168, and 29.41% calcium stearate based on the total weight of the antioxidant composition.

[0105] (2) Preparation of HDPE composition

[0106] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0107] The components and weight percentages of the antioxidant compositions in Examples 1-10 and Comparative Examples 1-3, as well as the amount of antioxidant composition added to HDPE, are listed in Table 1.

[0108] Comparative Example 1

[0109] (1) Preparation of antioxidant composition

[0110] Based on the total weight of the antioxidant composition, 23.46% hindered phenolic antioxidant 1010, 46.92% antioxidant 168, and 29.62% calcium stearate were mixed to obtain the antioxidant composition.

[0111] (2) Preparation of HDPE composition

[0112] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1300 ppm of the antioxidant composition from step (1) was added and mixed. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0113] Comparative Example 2

[0114] (1) Preparation of antioxidant composition

[0115] Based on the total weight of the antioxidant composition, 17.65% hindered phenolic antioxidant 3114, 52.94% antioxidant 168, and 29.41% calcium stearate were mixed to obtain the antioxidant composition.

[0116] (2) Preparation of HDPE composition

[0117] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 1700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0118] Comparative Example 3

[0119] (1) Preparation of antioxidant composition

[0120] Based on the total weight of the antioxidant composition, hindered phenolic antioxidant 1010 (3.7%), antioxidant 168 (66.67%), 626 (11.11%), and calcium stearate (18.52%) are mixed to obtain the antioxidant composition.

[0121] (2) Preparation of HDPE composition

[0122] HDPE (powder) with a melt index of 20 g / 10 min at 190 °C under a load of 2.16 kg was prepared using the Hostalen ACP process as the matrix. 2700 ppm of the antioxidant composition from step (1) was added and blended. HDPE composition granules were obtained by extrusion granulation at a temperature of 210 °C.

[0123] Table 1

[0124]

[0125]

[0126] Performance Test (Part 1):

[0127] The initial YI of the granulated HDPE granules, the YI of the injection-molded samples, and the yellow index after gas fumigation tests in Examples 1-10 and Comparative Examples 1-3 are shown in Table 2. YI was tested according to ASTM E313-2005; the gas fumigation test was conducted according to JIS L-0855. To shorten the testing time, the sample concentration was twice that of the standard, and the sample thickness was 1 mm.

[0128] Table 2. Initial YI of HDPE granules after granulation, YI of injection-molded samples, and yellow index after gas fumigation test.

[0129]

[0130]

[0131] As can be seen from Table 2, compared with Comparative Examples 1-3 which used hindered phenolic antioxidants as antioxidants, the high-density polyethylene resins obtained in Examples 1-10 of this application, which used hindered amine light stabilizers as antioxidants, not only had lower initial YI values ​​in the samples, but also lower YI changes after 3 and 6 days of fumigation. This indicates that the specific antioxidant composition used in this invention can give polyethylene materials a lower initial color and better resistance to fading after fumigation.

[0132] Performance Test (Part 2):

[0133] The injection-molded samples YI from Examples 1-10 and Comparative Examples 1-3, as well as YI after heat aging (tested according to ASTM E313-2005) and tensile properties (tested according to GB / T1040.2-2006), were tested. The results are shown in Table 3. The heat aging test was conducted at 100℃, and YI was tested according to ASTM E313-2005; the tensile properties were tested according to GB / T1040.2-2006.

[0134] Table 3. MFR after granulation, YI of injection-molded samples, YI after heat aging, and tensile properties.

[0135]

[0136] As shown in Table 3, after heat aging, the changes in YI of the polyethylene materials in Examples 1-10 were relatively small. The compositions in the examples did not contain hindered phenolic antioxidants, thus avoiding the impact of phenolic yellowing on the material's appearance and ensuring the long-term color stability of the high-density polyethylene material. Simultaneously, they effectively avoided the yellowing problem caused by nitrogen oxides encountered by hindered phenolic antioxidants. In particular, the changes in YI after heat aging in Examples 1, 2, 5, 6, and 8 were significantly lower than those in the corresponding comparative examples. The light stabilizers 944 and 2020 in Examples 3 and 4 both belong to the hexamethylenediamine piperidine series of triazine hindered amine light stabilizers, and their slightly higher ΔYI after heat aging may be related to the structure of these hindered amines.

[0137] In summary, considering the granulation YI of polyethylene resin, the initial YI of the sample, the yellow index after gas fumigation, and the yellow index after heat aging, the polyethylene resin materials prepared in Examples 1, 2, 5, 6, and 8 exhibit superior performance.

[0138] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A polymeric material composition comprising high-density polyethylene and an antioxidant composition, said antioxidant composition comprising: Hindered amine light stabilizers, phosphite antioxidants, and acid removers; By weight percentage, the antioxidant composition comprises 15%-25% hindered amine light stabilizer, 45%-55% phosphite antioxidant, and 25%-35% acid remover; wherein the acid remover is a metal stearate salt. 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 stabilizers contain the group shown in Formula I, and the triazine hindered amine light stabilizers contain the group shown in Formula II. Formula I Formula II In Formulas I and II, R1 and R2 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.

2. The polymer material composition according to claim 1, characterized in that, The triazine-based hindered amine light stabilizers include hexamethylenediamine piperidine series triazine-based hindered amine light stabilizers and butylamine piperidine series triazine-based hindered amine light stabilizers; the hexamethylenediamine piperidine series triazine-based hindered amine light stabilizers further contain the group shown in Formula III, and the butylamine piperidine series triazine-based hindered amine light stabilizers further contain the group shown in Formula IV. Formula III Formula IV In Formulas III and 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.

3. The polymer material composition according to claim 2, characterized in that, The ester-linked piperidine series hindered amine light stabilizer is selected from at least one of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol). The hexamethylenediamine-piperidine series of triazine hindered amine light stabilizers are selected from the polymerization products of 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]}, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine with 2,4,6-trichloro-1,3,5-triazine and N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinylamine. At least one of the following: poly[(6-morpholino-1,3,5-triazine-2,4-yl)-((2,2,6,6-tetramethyl-4-piperidinyl)imine)hexane-((2,2,6,6-tetramethyl-4-piperidinyl)imine)], N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and methylated polymers of morpholino-2,4,6-trichloro-1,3,5-triazine; The butylamine piperidine series of triazine hindered amine light stabilizers are selected from at least one of the following: 1,5,8,12-tetra[2,4-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-6-yl]-1,5,8,12-tetraazadodecane, N,N”-1,2-dimethylene-1,3-propanediamine polymer and 2,4,6-trichloro-1,3,5-triazine and N-butyl-2,2,6,6-tetramethyl-4-ammonium.

4. The polymeric material composition according to any one of claims 1-3, characterized in that, The phosphite antioxidants are selected from phosphite antioxidants having a 2,4-di-tert-butylbenzene or pentaerythritol structure.

5. The polymer material composition according to claim 4, characterized in that, The phosphite antioxidant is selected from at least one of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and pentaerythritol dioctadecyl phosphite.

6. The polymer material composition according to claim 1, characterized in that, The deacidifying agent is selected from at least one of zinc stearate, calcium stearate, and magnesium stearate.

7. The polymeric material composition according to any one of claims 1-3, characterized in that, The antioxidant composition comprises poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, tris(2,4-di-tert-butylphenyl) phosphite, and calcium stearate.

8. The polymer material composition according to claim 7, characterized in that, The antioxidant composition comprises, by weight percentage, 15-25% polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), 45-55% tris(2,4-di-tert-butylphenyl) phosphite and 25-35% calcium stearate.

9. The polymeric material composition according to any one of claims 1-3, characterized in that, The melt flow rate (MFR) of the high-density polyethylene at 190°C under a load of 2.16 kg is 10-40 g / 10 min.

10. The polymeric material composition according to claim 8, characterized in that, The melt flow rate (MFR) of the high-density polyethylene at 190°C under a load of 2.16 kg is 15-25 g / 10 min.

11. An ES fiber sheath material comprising the polymeric material composition according to any one of claims 1-10.

12. An ES fiber comprising a sheath and a core, said sheath comprising the polymeric material composition of any one of claims 1-10.

13. The use of the polymeric material composition according to any one of claims 1-10 in the production, processing, use, storage, and transportation of ES fibers.

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