A stabilizer composition, a polyethylene wire and cable special material and a preparation method thereof, and a polyethylene wire and cable

Abstract

This invention provides a stabilizer composition, a special material for polyethylene wires and cables, a method for preparing the same, and polyethylene wires and cables. The stabilizer composition provided by this invention comprises the following components in parts by weight: hindered phenolic stabilizers AO-1 and / or AO-2 0.10–0.15 parts; amine antioxidant AN-1 0.05–0.10 parts; thioester stabilizers DLTDP and / or 412S 0.03–0.10 parts; and phosphite antioxidant PS-1 0.02–0.05 parts; wherein the structures of the hindered phenolic stabilizers AO-1, ​​AO-2, amine antioxidant AN-1, and phosphite antioxidant PS-1 are shown below. This invention combines the above components in a certain proportion, allowing them to interact and effectively improve the antioxidant properties and stability of the product.

Description

Technical Field

[0001] This invention relates to the field of chemical technology, and in particular to a stabilizer composition, a special material for polyethylene wires and cables, a method for preparing the same, and polyethylene wires and cables. Background Technology

[0002] Wires and cables are widely used materials in electrical equipment, power, and communications. The main raw materials used in wire and cable manufacturing processes are PE and PVC. However, PVC is relatively unstable to heat and light, and it can produce allyl chloride during aging, posing environmental and health risks, and has therefore been banned and phased out. PE has become the mainstream material; for example, communication cables typically use HDPE for insulation and LLDPE for sheathing; optical cables mainly use HDPE and MDPE as sheathing materials.

[0003] The traditional method for modifying and processing materials for wires and cables involves: material preparation, mixing, feeding, extrusion, cooling, and pelletizing. The main processing machinery is a plastic extrusion granulator. The production principle of a plastic extrusion granulator is to use a high-temperature melting, plasticizing, and extrusion process to plasticize, shape, extrude, cool, and pelletize the plastic, thereby altering its physical, chemical, and mechanical properties. After polyethylene is uniformly mixed with various additives, it enters the barrel from the hopper. Under the action of the rotating screw, it is conveyed forward to the feeding section through the frictional shearing action of the inner wall of the barrel and the screw surface, and then fed into the extruder for melting and further uniform mixing. Through a multi-hole die, multiple strips are formed. After leaving the die, the strips are cooled by air or water and then cut into pellets by a rotating blade.

[0004] In the production of special materials for wires and cables, it is necessary to select appropriate plastic types and add suitable stabilizers to improve their oxidation induction period and service life. Furthermore, a scientific preparation method is required. The conventional processing method for special materials for wires and cables involves premixing polymer base materials and additives, then feeding the mixture into a screw extruder. The mixture is then extruded, cooled, and pelletized to obtain the product. Commonly used additives to improve stability include antioxidants 215 and 225. However, practical applications have shown that while the above method can improve antioxidant performance, it suffers from drawbacks such as high dosage, high cost, and generally limited effectiveness.

[0005] To overcome the above problems, existing technologies have attempted to adopt some measures. For example, CN10777852A discloses a special material for polyethylene wires and cables, which improves the oxidation resistance of polyethylene cables through a certain stabilizer composition. However, its improvement effect is limited, with the oxidation induction period (OIT) only above 25 minutes, and the highest reaching only 34.1 minutes. The effect is still unsatisfactory, and the processing stability is also poor. Summary of the Invention

[0006] In view of this, the present invention provides a stabilizer composition, a special material for polyethylene wires and cables, a method for preparing the same, and polyethylene wires and cables. The stabilizer composition provided by the present invention can effectively improve the oxidation resistance and processing stability of polyethylene wires and cables.

[0007] This invention provides a stabilizer composition comprising the following components in parts by weight:

[0008] Hindered phenolic stabilizers AO-1 and / or AO-2, 0.10~0.15 parts;

[0009] Amine antioxidant AN-1: 0.05~0.10 parts;

[0010] Thioester stabilizers DLTDP and / or 412S, 0.03~0.10 parts;

[0011] Phosphite antioxidant PS-1, 0.02~0.05 parts;

[0012] in:

[0013] The structures of the hindered phenolic stabilizers AO-1 and AO-2 are as follows:

[0014] Equation (AO-1),

[0015] Equation (AO-2);

[0016] The amine antioxidant AN-1 is selected from one or more compounds shown in the following formula:

[0017] Formula (AN-1);

[0018] Among them, R1 and R2 are independently selected from: hydrogen, octyl, and butyl;

[0019] The structure of the phosphite antioxidant PS-1 is as follows:

[0020] Formula (PS-1).

[0021] Preferably, the components include the following parts by weight:

[0022] Hindered phenolic stabilizer AO-1, ​​0.10~0.15 parts;

[0023] Amine antioxidant AN-1: 0.05~0.10 parts;

[0024] Thioester stabilizer DLTDP 0.05~0.10 parts;

[0025] Phosphite antioxidant PS-1, 0.02~0.05 parts;

[0026] or

[0027] The components include the following parts by weight:

[0028] 0.10 parts of hindered phenolic stabilizer AO-1;

[0029] Amine antioxidant AN-1: 0.05~0.10 parts;

[0030] Thioester stabilizer 412S 0.03 parts;

[0031] 0.02 parts of PS-1, a phosphite antioxidant;

[0032] or

[0033] The components include the following parts by weight:

[0034] 0.10 parts of hindered phenolic stabilizer AO-2;

[0035] Amine antioxidant AN-1: 0.05~0.10 parts;

[0036] Thioester stabilizer 412S 0.03 parts;

[0037] 0.02 parts of PS-1, a phosphite antioxidant.

[0038] Preferably, the components include the following parts by weight:

[0039] 0.10 parts of hindered phenolic stabilizer AO-1;

[0040] 0.05 parts of amine antioxidant AN-1;

[0041] 0.10 parts of DLTDP, a thioester stabilizer;

[0042] 0.05 parts of PS-1, a phosphite antioxidant;

[0043] or

[0044] The components include the following parts by weight:

[0045] 0.15 parts of hindered phenolic stabilizer AO-1;

[0046] 0.05 parts of amine antioxidant AN-1;

[0047] 0.05 parts of DLTDP, a thioester stabilizer;

[0048] 0.05 parts of PS-1, a phosphite antioxidant;

[0049] or

[0050] The components include the following parts by weight:

[0051] 0.10 parts of hindered phenolic stabilizer AO-1;

[0052] 0.05 parts of amine antioxidant AN-1;

[0053] Thioester stabilizer 412S 0.03 parts;

[0054] 0.02 parts of PS-1, a phosphite antioxidant;

[0055] or

[0056] The components include the following parts by weight:

[0057] 0.10 parts of hindered phenolic stabilizer AO-2;

[0058] 0.10 parts of amine antioxidant AN-1;

[0059] Thioester stabilizer 412S 0.03 parts;

[0060] 0.02 parts of PS-1, a phosphite antioxidant.

[0061] Preferably, the amine antioxidant AN-1 includes: diphenylamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, butyloctyldiphenylamine, and dioctyldiphenylamine.

[0062] This invention also provides a polyethylene wire and cable special material, the raw materials of which include the following components in parts by weight:

[0063] 100 parts of polyethylene;

[0064] 1-4 parts of peroxide crosslinking agent;

[0065] Antioxidant 0.1~0.3 parts;

[0066] The antioxidant is the stabilizer composition described in the above technical solution.

[0067] Preferably, the peroxide crosslinking agent is at least one of DCP, DHBP, and DTBP;

[0068] The polyethylene is LDPE.

[0069] This invention also provides a method for preparing the polyethylene wire and cable special material described in the above technical solution, comprising the following steps:

[0070] Polyethylene, peroxide crosslinking agent and antioxidant are added to a rotary flask, the rotary flask is evacuated, the rotation is turned on and the temperature is raised for vacuum rotation and heat preservation, to obtain polyethylene special material for wires and cables.

[0071] Preferably, the conditions for vacuum rotation heat preservation are: temperature 60~70℃, rotation speed 20~60 r / min, and time 1~2h.

[0072] The present invention also provides a polyethylene wire and cable special material prepared by the preparation method described in the above technical solution.

[0073] The present invention also provides a polyethylene wire and cable, the raw material of which is the polyethylene wire and cable special material described in the above technical solution.

[0074] The stabilizer composition provided by this invention combines the hindered phenolic stabilizers AO-1 and / or AO-2, the amine antioxidant AN-1, the thioester stabilizers DLTDP and / or 412S, and the phosphite antioxidant PS-1 in a certain proportion. Their interaction effectively improves the antioxidant properties and stability of the product. Simultaneously, this application also provides a method for preparing polyethylene wire and cable special material, processed using a blending method. Compared with conventional extrusion granulation methods, the stabilizer formulation of this invention is beneficial for improving the antioxidant properties and stability of the product, and eliminates the need for granulation, significantly reducing energy consumption and making it more energy-efficient and environmentally friendly, effectively reducing energy consumption in wire and cable material production.

[0075] The test results show that the stabilizer composition formulation provided by the present invention can enable the product to achieve an OIT of more than 44 min and an MI of more than 2.01 g / 10 min, exhibiting excellent antioxidant properties and stability. Detailed Implementation

[0076] This invention provides a stabilizer composition comprising the following components in parts by weight:

[0077] Hindered phenolic stabilizers AO-1 and / or AO-2, 0.10~0.15 parts;

[0078] Amine antioxidant AN-1: 0.05~0.10 parts;

[0079] Thioester stabilizers DLTDP and / or 412S, 0.03~0.10 parts;

[0080] Phosphite antioxidant PS-1, 0.02~0.05 parts;

[0081] in:

[0082] The structures of the hindered phenolic stabilizers AO-1 and AO-2 are as follows:

[0083] Equation (AO-1),

[0084] Equation (AO-2);

[0085] The amine antioxidant AN-1 is selected from one or more compounds shown in the following formula:

[0086] Formula (AN-1);

[0087] Among them, R1 and R2 are independently selected from: hydrogen, octyl, and butyl;

[0088] The structure of the phosphite antioxidant PS-1 is as follows:

[0089] Formula (PS-1).

[0090] The stabilizer composition provided by the present invention combines the above-mentioned hindered phenolic stabilizers AO-1 and / or AO-2, amine antioxidant AN-1, thioester stabilizers DLTDP and / or 412S, and phosphite antioxidant PS-1 in a certain proportion, which interact to effectively improve the antioxidant properties and stability of the product.

[0091] In this invention, the hindered phenolic stabilizer is AO-1 and / or AO-2, wherein AO-1 is isooctanol ester of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and AO-2 is tridecyl ester of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and their structures are as follows:

[0092] Equation (AO-1),

[0093] Equation (AO-2).

[0094] This invention does not impose any special restrictions on the source of the two hindered phenolic stabilizers mentioned above; they can be commercially available products or prepared according to methods known in the art. For example, AO-1 of the above structure is a commercially available liquid hindered phenolic antioxidant. In this invention, for the sake of intuitive and convenient identification of substances, the names AO-1 and AO-2 are self-named / labeled in this invention. AO generally represents a hindered phenolic stabilizer. This invention involves two structures, distinguished by serial numbers 1 and 2, and therefore respectively denoted as AO-1 and AO-2.

[0095] In this invention, the amount of the hindered phenolic stabilizer is 0.10 to 0.15 parts, specifically 0.10 parts, 0.11 parts, 0.12 parts, 0.13 parts, 0.14 parts, or 0.15 parts.

[0096] In this invention, the amine antioxidant AN-1 is selected from one or more compounds shown in the following formula:

[0097] Formula (AN-1);

[0098] R1 and R2 are independently selected from: hydrogen, octyl, and butyl.

[0099] In this invention, preferably, the amine antioxidant AN-1 comprises: diphenylamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, butyloctyldiphenylamine, and dioctyldiphenylamine. More preferably, the mass percentages of each component in the amine antioxidant AN-1 are as follows: diphenylamine 0.21%~0.96%, monobutyldiphenylamine 1.58%~13.50%, dibutyldiphenylamine 4.3%~8.73%, monooctyldiphenylamine 17.99%~70.94%, butyloctyldiphenylamine 13.05%~38.37%, and dioctyldiphenylamine 6.53%~24.73%. In some embodiments of the present invention, the amine antioxidant AN-1 comprises: 0.96% diphenylamine, 3.32% monobutyldiphenylamine, 4.3% dibutyldiphenylamine, 70.94% monooctyldiphenylamine, 13.05% butyloctyldiphenylamine, and 6.53% dioctyldiphenylamine. In this invention, the amine antioxidant AN-1 can be prepared according to the preparation method disclosed in patent application CN103709046B. Similar to AO-1 mentioned above, for the sake of intuitive and convenient identification of the substance, the above-mentioned AN-1 is also a name / labeling of the present invention.

[0100] In this invention, the amount of the amine antioxidant AN-1 is 0.05~0.10 parts, specifically 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, or 0.10 parts.

[0101] In this invention, the thioester stabilizers are DLTDP and / or 412S, both of which are known substances (i.e., DLTDP and 421S are known product names). The chemical name of stabilizer DLTDP is dodecayl thiodipropionate, and the chemical name of stabilizer 412S (also known as antioxidant TH-412S) is pentaerythritol tetra(3-lauryl thiopropionate). Their structures are as follows:

[0102] Stabilizer DLTDP:

[0103]

[0104] Stabilizer 412S:

[0105]

[0106] In this invention, the amount of the thioester stabilizer is 0.03 to 0.10 parts, specifically 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, or 0.10 parts.

[0107] In this invention, the chemical name of the phosphite antioxidant PS-1 is tris(m-pentadecanylphenyl) phosphite, and its structure is as follows:

[0108] Formula (PS-1).

[0109] This invention does not impose any special restrictions on the source of the phosphite antioxidant PS-1; it can be prepared according to known methods. Similar to AO-1 mentioned earlier, for the sake of clarity and convenience, PS-1 is also the name / labeling used by this invention.

[0110] In this invention, the amount of the phosphite antioxidant PS-1 is 0.02 to 0.05 parts, specifically 0.02 parts, 0.03 parts, 0.04 parts, or 0.05 parts.

[0111] In this invention, preferably, the stabilizer composition comprises the following components in parts by weight:

[0112] Hindered phenolic stabilizer AO-1, ​​0.10~0.15 parts;

[0113] Amine antioxidant AN-1: 0.05~0.10 parts;

[0114] Thioester stabilizer DLTDP 0.05~0.10 parts;

[0115] Phosphite antioxidant PS-1, 0.02~0.05 parts;

[0116] or

[0117] The components include the following parts by weight:

[0118] 0.10 parts of hindered phenolic stabilizer AO-1;

[0119] Amine antioxidant AN-1: 0.05~0.10 parts;

[0120] Thioester stabilizer 412S 0.03 parts;

[0121] 0.02 parts of PS-1, a phosphite antioxidant;

[0122] or

[0123] The components include the following parts by weight:

[0124] 0.10 parts of hindered phenolic stabilizer AO-2;

[0125] Amine antioxidant AN-1: 0.05~0.10 parts;

[0126] Thioester stabilizer 412S 0.03 parts;

[0127] 0.02 parts of PS-1, a phosphite antioxidant.

[0128] More preferably, in this invention, the stabilizer composition comprises the following components in parts by weight:

[0129] 0.10 parts of hindered phenolic stabilizer AO-1;

[0130] 0.05 parts of amine antioxidant AN-1;

[0131] 0.10 parts of DLTDP, a thioester stabilizer;

[0132] 0.05 parts of PS-1, a phosphite antioxidant;

[0133] or

[0134] The components include the following parts by weight:

[0135] 0.15 parts of hindered phenolic stabilizer AO-1;

[0136] 0.05 parts of amine antioxidant AN-1;

[0137] 0.05 parts of DLTDP, a thioester stabilizer;

[0138] 0.05 parts of PS-1, a phosphite antioxidant;

[0139] or

[0140] The components include the following parts by weight:

[0141] 0.10 parts of hindered phenolic stabilizer AO-1;

[0142] 0.05 parts of amine antioxidant AN-1;

[0143] Thioester stabilizer 412S 0.03 parts;

[0144] 0.02 parts of PS-1, a phosphite antioxidant;

[0145] or

[0146] The components include the following parts by weight:

[0147] 0.10 parts of hindered phenolic stabilizer AO-2;

[0148] 0.10 parts of amine antioxidant AN-1;

[0149] Thioester stabilizer 412S 0.03 parts;

[0150] 0.02 parts of PS-1, a phosphite antioxidant.

[0151] The present invention does not impose any particular limitations on the preparation method of the stabilizer composition; simply mixing the components evenly is sufficient. The stabilizer composition obtained by the present invention is a liquid antioxidant product.

[0152] Regarding antioxidants and stabilizers alone, there are countless types in the prior art. The stabilizer composition provided by this invention combines the above-mentioned hindered phenolic stabilizers AO-1 and / or AO-2, amine antioxidants AN-1, thioester stabilizers DLTDP and / or 412S, and phosphite antioxidants PS-1 in a certain proportion. Through their interaction, they can effectively improve the antioxidant properties and stability of the product.

[0153] This invention also provides a polyethylene wire and cable special material, the raw materials of which include the following components in parts by weight:

[0154] 100 parts of polyethylene;

[0155] 1-4 parts of peroxide crosslinking agent;

[0156] Antioxidant 0.1~0.3 parts;

[0157] The antioxidant is the stabilizer composition described in the above technical solution.

[0158] In this invention, the polyethylene (PE) is preferably low-density polyethylene (LDPE). This invention does not impose any special restrictions on the source of the polyethylene; any commercially available product is acceptable. In some embodiments of this invention, the polyethylene is LDPE, specifically Qilu Petrochemical 2102TN00.

[0159] In this invention, the peroxide crosslinking agent is preferably at least one selected from DCP (dicumyl peroxide), DHBP (2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane), and DTBP (di-tert-butyl peroxide). In this invention, based on 100 parts by weight of polyethylene, the amount of the peroxide crosslinking agent is 1 to 4 parts, specifically 1 part, 2 parts, 3 parts, or 4 parts.

[0160] In this invention, the antioxidant is the stabilizer composition described in the above technical solution, which will not be repeated here. In this invention, based on 100 parts by weight of polyethylene, the amount of antioxidant is 0.1 to 0.3 parts, specifically 0.1 parts, 0.2 parts, or 0.3 parts.

[0161] This invention also provides a method for preparing the polyethylene wire and cable special material described in the above technical solution, comprising the following steps:

[0162] Polyethylene, peroxide crosslinking agent and antioxidant are added to a rotary flask, the rotary flask is evacuated, the rotation is turned on and the temperature is raised for vacuum rotation and heat preservation, to obtain polyethylene special material for wires and cables.

[0163] The types and amounts of polyethylene, peroxide crosslinking agent and antioxidant are consistent with those described in the previous technical solution, and will not be repeated here.

[0164] In this invention, after adding polyethylene, a peroxide crosslinking agent, and an antioxidant to a rotating flask, the flask is evacuated to remove as much air as possible. Then, the rotating flask is turned on and kept rotating, and the temperature is increased for vacuum rotational heat preservation. The preferred conditions for vacuum rotational heat preservation are: temperature 60-70°C, rotation speed 20-60 r / min, and time 1-2 h. Specifically, the temperature can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, or 70°C, more preferably 60-65°C. The rotation speed can be 20 r / min, 30 r / min, 40 r / min, 50 r / min, or 60 r / min. The time can be 1 h, 1.5 h, or 2 h, more preferably 1-1.5 h. In this invention, the temperature is raised to the target temperature to allow the peroxide crosslinking agent and antioxidant to fully melt and adhere evenly to the PE particles. The particles are then kept at the target temperature and rotated under vacuum for a certain period of time to allow the peroxide and antioxidant composition to completely penetrate into the PE particles. After cooling and discharge, polyethylene wire and cable special material is obtained.

[0165] To achieve the above technical solutions, this invention requires studying whether there are any adverse interactions between the peroxide crosslinking agent and the antioxidant, and experimentally analyzing the feasibility and effectiveness of various antioxidant formulations and peroxide crosslinking agents penetrating into PE particles under certain conditions. Compared with conventional extrusion granulation methods, the above processing method of this invention is beneficial to improving the antioxidant properties and stability of the product. The applicant's research found that if extrusion granulation is used, the peroxide crosslinking agent is prone to prematurely consuming the antioxidant during high-temperature extrusion processing, and will also prematurely act on PE, reducing its performance. Therefore, it is necessary to minimize the contact between the peroxide crosslinking agent, antioxidant, and PE during high-temperature processing. The peroxide crosslinking agent is added in zone 5 and discharged in zone 7. To further reduce the mutual loss between the peroxide crosslinking agent and antioxidant, and the premature action of DCP and PE, the extrusion temperature is strictly controlled. Compared with extrusion granulation, the above processing method of this invention, combined with the specific antioxidant formulation of this invention, not only improves the antioxidant properties and stability of the product, but also eliminates the need for granulation, significantly reducing energy consumption, making it more energy-efficient and environmentally friendly, and effectively reducing energy consumption in the production of wire and cable materials.

[0166] The present invention also provides a polyethylene wire and cable special material prepared by the preparation method described in the above technical solution.

[0167] This invention also provides a polyethylene wire and cable, characterized in that its raw material is the polyethylene wire and cable special material described in the above-mentioned technical solution or the polyethylene wire and cable special material described in the above-mentioned technical solution. The polyethylene wire and cable is a cross-linked polyethylene cable. This invention does not impose any special limitations on the preparation method of the polyethylene wire and cable using the polyethylene wire and cable special material; any conventional method in the art is acceptable.

[0168] The test results show that the stabilizer composition formulation provided by the present invention can enable the product to achieve an OIT of more than 44 min and an MI of more than 2.01 g / 10 min, exhibiting excellent antioxidant properties and stability.

[0169] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0170] Example 1

[0171] 1. Stabilizer composition formulation:

[0172] 0.10 parts of hindered phenolic stabilizer AO-1;

[0173] 0.05 parts of amine antioxidant AN-1;

[0174] 0.10 parts of DLTDP, a thioester stabilizer;

[0175] 0.05 parts of PS-1, a phosphite antioxidant;

[0176] The amine antioxidant AN-1 was prepared according to the preparation method in Example 3 of patent CN103709046B, as follows:

[0177] 380g of diphenylamine, 302g of diisobutylene, 57g of 2% phosphotungstic acid-supported activated clay catalyst, and 2g of hydroquinone as a polymerization inhibitor were added to a 2L high-pressure reactor. The reactor was sealed, and the temperature was raised to 120℃ for alkylation reaction. The initial pressure was 0.4MPa, and the pressure was gradually reduced as the reaction proceeded. The alkylation reaction lasted for 6 hours, and then the temperature was raised to 180℃ for cracking reaction. The reaction pressure was 0.3MPa, and the cracking reaction lasted for 2 hours. The temperature was then lowered to 90℃. The pressure inside the reactor was reduced from 0℃ to approximately 0.03 MPa to remove residual moisture and low molecular weight alkanes. The temperature was then lowered to 50℃, and the catalyst was removed by filtration to obtain 650g of a pale yellow liquid antioxidant. Its composition is: 0.96% diphenylamine, 3.32% monobutyldiphenylamine, 4.3% dibutyldiphenylamine, 70.94% monooctyldiphenylamine, 13.05% butyloctyldiphenylamine, and 6.53% dioctyldiphenylamine.

[0178] 2. Raw material formula for polyethylene wire and cable special material:

[0179] Polyethylene (LDPE, Qilu Petrochemical 2102TN00, basic melt index 2.2) 100g;

[0180] Peroxide crosslinking agent DCP 1.8g;

[0181] Antioxidant 0.3g;

[0182] The antioxidant is the aforementioned stabilizer composition.

[0183] 3. Preparation of polyethylene wire and cable special material (experimental group method):

[0184] Rotary infiltration method:

[0185] Polyethylene, peroxide crosslinking agent and antioxidant are added to a rotary flask, vacuumed in a 70℃ water bath and rotated at 40r / min for 1.5h. Then, the mixture is cooled and discharged to obtain polyethylene material for wires and cables.

[0186] 4. Preparation of polyethylene wire and cable special material (control group method):

[0187] Extrusion granulation method:

[0188] Twin-screw extruder: SHJ-36 co-rotating twin-screw extruder; polyethylene, peroxide crosslinking agent and antioxidant are mixed evenly, and extruded and granulated according to the extrusion processing parameters in Table 1 to obtain polyethylene wire and cable special material.

[0189] Table 1: Process parameters for extrusion granulation

[0190]

[0191] Example 2

[0192] 1. Stabilizer composition formulation:

[0193] 0.15 parts of hindered phenolic stabilizer AO-1;

[0194] 0.05 parts of amine antioxidant AN-1;

[0195] 0.05 parts of DLTDP, a thioester stabilizer;

[0196] 0.05 parts of PS-1, a phosphite antioxidant;

[0197] The amine antioxidant AN-1 is the same as in Example 1.

[0198] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, only the type of antioxidant is replaced accordingly.

[0199] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0200] 4. Preparation of polyethylene wire and cable special material (control group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0201] Example 3

[0202] 1. Stabilizer composition formulation:

[0203] 0.10 parts of hindered phenolic stabilizer AO-1;

[0204] 0.05 parts of amine antioxidant AN-1;

[0205] Thioester stabilizer 412S 0.03 parts;

[0206] 0.02 parts of PS-1, a phosphite antioxidant;

[0207] The amine antioxidant AN-1 is the same as in Example 1.

[0208] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, only the type of antioxidant is replaced accordingly.

[0209] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0210] 4. Preparation of polyethylene wire and cable special material (control group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0211] Example 4

[0212] 1. Stabilizer composition formulation:

[0213] 0.10 parts of hindered phenolic stabilizer AO-2;

[0214] 0.10 parts of amine antioxidant AN-1;

[0215] Thioester stabilizer 412S 0.03 parts;

[0216] 0.02 parts of PS-1, a phosphite antioxidant;

[0217] The amine antioxidant AN-1 is the same as in Example 1.

[0218] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, only the type of antioxidant is replaced accordingly.

[0219] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0220] 4. Preparation of polyethylene wire and cable special material (control group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0221] Blank example

[0222] 1. No antioxidants

[0223] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, except that antioxidants are not added.

[0224] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as Example 1, except that antioxidants are not added.

[0225] 4. Preparation of polyethylene wire and cable special material (control group method): Same as Example 1, except that antioxidants are not added.

[0226] Comparative Example 1

[0227] 1. Stabilizer composition formulation:

[0228] Antioxidant 1010, 0.10 parts;

[0229] Antioxidant 168 0.20 parts.

[0230] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, only the type of antioxidant is replaced accordingly.

[0231] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0232] 4. Preparation of polyethylene wire and cable special material (control group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0233] Comparative Example 2

[0234] 1. Stabilizer composition formulation:

[0235] Antioxidant 1076, 0.06 parts;

[0236] Antioxidant DSTDP 0.24 parts.

[0237] 2. Raw material formula for polyethylene wire and cable special material: Same as in Example 1, only the type of antioxidant is replaced accordingly.

[0238] 3. Preparation of polyethylene wire and cable special material (experimental group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0239] 4. Preparation of polyethylene wire and cable special material (control group method): Same as in Example 1, except that the type of antioxidant is replaced accordingly.

[0240] Test example:

[0241] The oxidation induction period (OIT, in min) and melt index (MI, in g / 10 min) of the polyethylene wire and cable special materials obtained in Examples 1-4, blank examples, and comparative examples 1-2 were tested respectively. The results are shown in Table 2.

[0242] Table 2: Test Results

[0243]

[0244] As can be seen from the test results in Table 2, the stabilizer composition formulations of Examples 1-4 of the present invention can achieve an OIT of over 44 min, greatly improving the antioxidant properties. The MI reaches over 2.01 g / 10 min. It is known in the art that the melt index of polyethylene decreases with increasing aging degree because polyethylene is prone to cross-linking during the aging process. Therefore, the higher the melt index after mixing with the formulation, the better the stability of the formulation. Thus, Examples 1-4 of the present invention greatly improve the stability.

[0245] Meanwhile, as shown in Comparative Examples 1-2, when using the conventional extrusion granulation method, the product's OIT reaches over 31.8 min and MI reaches over 1.9 g / 10 min; however, when using the rotary blending method, the product's OIT is below 26.3 min and MI is below 1.91 g / 10 min, indicating a significant decrease in antioxidant properties and stability. Comparative Example 1, in particular, uses a combination of antioxidants 1010 and 168. These two are recognized in the field as commonly used antioxidants with good antioxidant effects. However, the test results show that while conventional extrusion granulation does produce some antioxidant properties, the blending method reduces both antioxidant properties and stability. This demonstrates that not all antioxidant formulations are suitable for the blending method and can achieve good results.

[0246] As can be seen from Examples 1-4, when using extrusion granulation, the product's OIT is below 34.3 min and MI is below 1.92 g / 10 min; while when using rotary mixing, the product's OIT reaches above 44 min and MI reaches above 2.01 g / 10 min, significantly improving antioxidant properties and stability. Therefore, the stabilizer composition formulation of the present invention is suitable for the mixing method to achieve good results. Among Examples 1-4, the stabilizer composition sample of Example 4 has the highest OIT and MI, achieving the best effect.

[0247] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A method for preparing a polyethylene wire and cable special material, characterized in that, Includes the following steps: 100 parts by weight of polyethylene, 1-4 parts by weight of peroxide crosslinking agent and 0.1-0.3 parts by weight of antioxidant are added to a rotary flask. The rotary flask is evacuated, the rotation is turned on and the temperature is raised for vacuum rotation and heat preservation to obtain polyethylene wire and cable special material. The conditions for vacuum rotation heat preservation are: temperature 60~70℃, rotation speed 20~60 r / min, and time 1~2h. The antioxidant is a stabilizer composition, consisting of the following components in parts by weight: Hindered phenolic stabilizers AO-1 and / or AO-2, 0.10~0.15 parts; Amine antioxidant AN-1: 0.05~0.10 parts; Thioester stabilizers DLTDP and / or 412S, 0.03~0.10 parts; Phosphite antioxidant PS-1, 0.02~0.05 parts; in: The structures of the hindered phenolic stabilizers AO-1 and AO-2 are as follows: Equation (AO-1), Equation (AO-2); The amine antioxidant AN-1 is selected from one or more compounds shown in the following formula: Formula (AN-1); Among them, R1 and R2 are independently selected from: hydrogen, octyl, and butyl; The structure of the phosphite antioxidant PS-1 is as follows: Formula (PS-1).

2. The preparation method according to claim 1, characterized in that, The stabilizer composition comprises the following components in parts by weight: Hindered phenolic stabilizer AO-1, ​​0.10~0.15 parts; Amine antioxidant AN-1: 0.05~0.10 parts; Thioester stabilizer DLTDP 0.05~0.10 parts; Phosphite antioxidant PS-1, 0.02~0.05 parts; or The components include the following parts by weight: 0.10 parts of hindered phenolic stabilizer AO-1; Amine antioxidant AN-1: 0.05~0.10 parts; Thioester stabilizer 412S 0.03 parts; 0.02 parts of PS-1, a phosphite antioxidant; or The components include the following parts by weight: 0.10 parts of hindered phenolic stabilizer AO-2; Amine antioxidant AN-1: 0.05~0.10 parts; Thioester stabilizer 412S 0.03 parts; 0.02 parts of PS-1, a phosphite antioxidant.

3. The preparation method according to claim 1 or 2, characterized in that, The stabilizer composition comprises the following components in parts by weight: 0.10 parts of hindered phenolic stabilizer AO-1; 0.05 parts of amine antioxidant AN-1; 0.10 parts of DLTDP, a thioester stabilizer; 0.05 parts of PS-1, a phosphite antioxidant; or The components include the following parts by weight: 0.15 parts of hindered phenolic stabilizer AO-1; 0.05 parts of amine antioxidant AN-1; 0.05 parts of DLTDP, a thioester stabilizer; 0.05 parts of PS-1, a phosphite antioxidant; or The components include the following parts by weight: 0.10 parts of hindered phenolic stabilizer AO-1; 0.05 parts of amine antioxidant AN-1; Thioester stabilizer 412S 0.03 parts; 0.02 parts of PS-1, a phosphite antioxidant; or The components include the following parts by weight: 0.10 parts of hindered phenolic stabilizer AO-2; 0.10 parts of amine antioxidant AN-1; Thioester stabilizer 412S 0.03 parts; 0.02 parts of PS-1, a phosphite antioxidant.

4. The preparation method according to claim 1, characterized in that, The amine antioxidant AN-1 includes: diphenylamine, monobutyldiphenylamine, dibutyldiphenylamine, monooctyldiphenylamine, butyloctyldiphenylamine, and dioctyldiphenylamine.

5. The preparation method according to claim 1, characterized in that, The peroxide crosslinking agent is at least one of DCP, DHBP and DTBP; The polyethylene is LDPE.

6. A polyethylene wire and cable material prepared by any one of claims 1 to 5.

7. A polyethylene wire and cable, characterized in that, The raw materials for its preparation are polyethylene wire and cable special materials prepared by any one of claims 1 to 5 or polyethylene wire and cable special materials as described in claim 6.

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