Additive composition for polypropylene-based material, polypropylene-based cable material and preparation method thereof, and polypropylene-based cable

Abstract

This invention provides an additive composition for polypropylene-based materials, a polypropylene-based cable compound, a method for preparing the same, and a polypropylene-based cable. The additive composition for polypropylene-based materials provided by this invention is obtained by combining specific hindered phenolic compounds, hindered amine compounds, phosphite compounds, metal passivators, and lubricants in a certain proportion. These components work together and synergistically to protect the polypropylene macromolecular chains, reduce the degradation of polypropylene molecular chains in the presence of oxygen and light, and significantly improve the anti-aging properties of the polypropylene-based cable compound. The oxidation induction period of the polypropylene-based cable compound at 200°C is increased by more than three times. Simultaneously, the additive composition has a minimal impact on the polypropylene-based cable compound, meeting the electrical performance requirements of insulated cables. Furthermore, the additive composition requires a low dosage in actual use, effectively reducing costs.

Description

Technical Field

[0001] This invention relates to the chemical industry, and in particular to an additive composition for polypropylene-based materials, a polypropylene-based cable material and its preparation method, and a polypropylene-based cable. Background Art

[0002] Polypropylene (PP)-based thermoplastic insulation materials have advantages such as no need for crosslinking, no introduction of crosslinking byproducts, and melt reusability. They also possess excellent insulation and heat resistance properties comparable to crosslinked polyethylene (XLPE), making them a recognized environmentally friendly alternative to XLPE for cable insulation and a primary insulation material for high-voltage DC cables. Compared to traditional XLPE, PP offers stronger insulation performance, better thermal stability, relatively lower prices, and simpler production processes. Polypropylene production does not require crosslinking treatment or degassing, and its environmentally friendly and biodegradable nature promotes carbon reduction, emission reduction, and recycling. It offers unique advantages in simplifying production processes, shortening production cycles, reducing costs, and increasing production speed.

[0003] Polyolefin materials undergo thermal or photo-oxidation reactions during use due to the influence of oxygen in the air and ultraviolet rays from sunlight. This deteriorates the physical and mechanical properties of polyolefin products, causing them to prematurely lose their original functions and usability. Oxidation induction period (OIT) is a relative measure of a material's resistance to oxidative decomposition and can be used to evaluate the material's own stabilization level.

[0004] Adding antioxidants and light stabilizers to plastic materials can effectively inhibit or reduce the rate of thermo-oxidative and photo-oxidative aging of plastic macromolecules, significantly improve the heat and light resistance of plastic materials, delay the degradation and aging process of plastic materials, and extend the service life of plastic products.

[0005] Research on polypropylene-based insulated cable materials mainly focuses on improving the inherent rigidity, poor toughness, and poor low-temperature impact resistance of polypropylene through chemical copolymerization or material blending modification, thereby meeting the insulation mechanical performance requirements of high-voltage DC cables. Currently, the stabilizer combination used is B215, but it suffers from problems such as high dosage and cost, and its effect on improving the anti-aging properties of polypropylene is unsatisfactory. Summary of the Invention

[0006] In view of this, the present invention provides an additive composition for polypropylene-based materials, a polypropylene-based cable material, a method for preparing the same, and a polypropylene-based cable. The additive composition for polypropylene-based materials provided by the present invention can effectively improve the anti-aging properties of polypropylene-based cable materials while ensuring their electrical properties, and it is used in small quantities and has low cost.

[0007] This invention provides an additive composition for polypropylene-based materials, comprising the following components by weight percentage:

[0008]

[0009] Preferably, the hindered phenolic compound is at least one selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate.

[0010] Preferably, the hindered amine compound is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944 and light stabilizer 2020.

[0011] Preferably, the phosphite compound is at least one of tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol diphosphite (2,4-di-tert-butylphenol).

[0012] Preferably, the metal passivating agent is BASF MD1024.

[0013] Preferably, the lubricant is at least one selected from calcium stearate, zinc stearate, and magnesium stearate.

[0014] Preferably, the polypropylene-based material is a polypropylene-based cable material.

[0015] The present invention also provides a polypropylene-based cable material, wherein the additives used are the polypropylene-based material additive composition described in the above technical solution.

[0016] The present invention also provides a method for preparing the polypropylene-based cable material described in the above technical solution, comprising the following steps:

[0017] The polypropylene-based cable base material and additive composition are premixed, then fed into a twin-screw extruder for shearing and extrusion, followed by stranding, air cooling and pelletizing to obtain the polypropylene-based cable material.

[0018] The additive composition is the polypropylene-based material additive composition described in the above technical solution.

[0019] The present invention also provides a polypropylene-based cable, which is made from the polypropylene-based cable material described in the above technical solution.

[0020] The additive composition for polypropylene-based materials provided by this invention is obtained by combining specific hindered phenolic compounds, hindered amine compounds, phosphite compounds, metal passivators, and lubricants in a certain proportion. These components work together and synergistically to protect the polypropylene macromolecular chains, reduce the degradation of polypropylene molecular chains in the presence of oxygen and light, and significantly improve the anti-aging properties of polypropylene-based cable materials. The oxidation induction period of polypropylene-based cable materials at 200°C is increased by more than three times. Simultaneously, this additive composition has a minimal impact on polypropylene-based cable materials, meeting the electrical performance requirements of insulated cables. Furthermore, in actual use, the dosage of the above additive composition is less than 0.5% of the mass of the polypropylene-based material, which is low and effectively reduces costs. Detailed Implementation

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0022] In this article, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions that include the listed features.

[0023] The term “and / or” as used herein includes any and all combinations of one or more of the related listed items.

[0024] In this document, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0025] In this article, when referring to units for data ranges, if the unit is only followed by the right endpoint, it indicates that the units for the left and right endpoints are the same. For example, 150~280℃ means that the units for the left endpoint "150" and the right endpoint "280" are both in℃.

[0026] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0027] This invention provides an additive composition for polypropylene-based materials, comprising the following components by weight percentage:

[0028]

[0029] In this invention, the hindered phenolic compound is preferably at least one selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (i.e., antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (i.e., antioxidant 1076), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid (i.e., antioxidant 3114), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (i.e., antioxidant 1330), and tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate (i.e., antioxidant 1790). These antioxidants may be derived from BASF. In this invention, the amount of the hindered phenolic compound is 10% to 40%, specifically 10%, 15%, 19.6%, 20%, 25%, 30%, 35%, 39.2%, and 40%.

[0030] In this invention, the hindered amine compound is preferably at least one selected from light stabilizer 770, light stabilizer 622, light stabilizer 944, and light stabilizer 2020. These light stabilizers can be sourced from Beijing Tiangang. In this invention, the amount of the hindered amine compound used is 10% to 40%, specifically 10%, 15%, 19.6%, 20%, 25%, 30%, 35%, 39.2%, and 40%.

[0031] In this invention, the phosphite compound is preferably at least one selected from tris(2,4-di-tert-butylphenyl) phosphite (i.e., antioxidant 168) and pentaerythritol diphosphite (i.e., antioxidant 626). These antioxidants may be derived from BASF. In this invention, the amount of the phosphite compound used is 10% to 60%, specifically 10%, 15%, 19.6%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and 60%.

[0032] In this invention, the metal passivating agent is preferably BASF MD1024. The amount of the metal passivating agent used in this invention is 1% to 5%, specifically 1%, 2%, 3%, 4%, or 5%.

[0033] In this invention, the lubricant is preferably at least one selected from calcium stearate, zinc stearate, and magnesium stearate. The amount of the lubricant used in this invention is 1% to 25%, specifically 1%, 5%, 10%, 15%, 19.6%, 20%, and 25%.

[0034] In this invention, the amount of each of the above components is preferably 100%.

[0035] In one embodiment of the present invention, the additive composition has the following composition:

[0036]

[0037] In another embodiment of the present invention, the additive composition has the following composition:

[0038]

[0039] In another embodiment of the present invention, the additive composition has the following composition:

[0040]

[0041] In another embodiment of the present invention, the additive composition has the following composition:

[0042]

[0043] In this invention, the additive composition for polypropylene-based materials is preferably used at a rate of less than 0.5% of the mass of the polypropylene-based material, more preferably at a rate of 0.2% to 0.4%, which is a relatively low amount.

[0044] In this invention, the polypropylene-based material is preferably a polypropylene-based cable material.

[0045] The additive composition for polypropylene-based materials provided by this invention is obtained by combining specific hindered phenolic compounds, hindered amine compounds, phosphite compounds, metal passivators, and lubricants in a certain proportion. These components work together and synergistically to protect the polypropylene macromolecular chains, reduce the degradation of polypropylene molecular chains in the presence of oxygen and light, and significantly improve the anti-aging properties of polypropylene-based cable materials. The oxidation induction period of polypropylene-based cable materials at 200°C is increased by more than three times. Simultaneously, this additive composition has a minimal impact on polypropylene-based cable materials, meeting the electrical performance requirements of insulated cables. Furthermore, in actual use, the dosage of the above additive composition is less than 0.5% of the mass of the polypropylene-based material, which is low and effectively reduces costs.

[0046] The present invention also provides a polypropylene-based cable material, wherein the additives used are the polypropylene-based material additive composition described in the above technical solution.

[0047] The present invention also provides a method for preparing polypropylene-based cable material as described in the above technical solution, comprising the following steps: premixing polypropylene-based cable material and additive composition, then feeding it into a twin-screw extruder for shearing and extrusion, and then subjecting it to stranding, air cooling and pelletizing to obtain polypropylene-based cable material; wherein, the additive composition is the additive composition for polypropylene-based materials described in the above technical solution.

[0048] In this invention, the polypropylene-based cable base material is not particularly limited and can be any conventional polypropylene-based cable base material in the art. In this invention, the premixing can be carried out in a mixer, specifically a high-speed mixer. Premixing ensures that all the above materials are thoroughly mixed. The mixed material is then fed into a twin-screw extruder by a feeder. After being sheared and blended by the twin-screw extruder, the material is extruded from the die head, then stretched, air-cooled, and pelletized to obtain the polypropylene-based cable material. In this invention, the screw temperature of each section of the twin-screw extruder is preferably controlled between 150 and 280°C. The feeding frequency is preferably 5 to 45 Hz, specifically 5 Hz, 10 Hz, 15 Hz, 20 Hz, 25 Hz, 30 Hz, 35 Hz, 40 Hz, and 45 Hz. The preferred rotational speed of the twin-screw extruder is 60–150 rpm, specifically 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, and 150 rpm. Through the above preparation process, masterbatch, i.e., polypropylene-based cable material, is obtained.

[0049] The present invention also provides a polypropylene-based cable, which is made from the polypropylene-based cable material described in the above technical solution.

[0050] 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.

[0051] Examples 1-4 and Comparative Examples 1-5

[0052] 1. Raw materials

[0053] The additive composition formulations of Comparative Examples 1-5 and Examples 1-4 correspond to samples 0# to 8# in Table 1, respectively. The amounts of each component in the table are in parts by mass.

[0054] Table 1: Additive composition formulations of Comparative Examples 1-5 and Examples 1-4

[0055]

[0056] 2. Preparation

[0057] Polypropylene-based cable base material (i.e., polypropylene) and additive composition are premixed in a high-speed mixer according to a certain ratio. The mixed material is fed into a twin-screw extruder by a feeder. After being sheared and blended by the twin-screw extruder, the material is extruded from the die head, and after being stretched, air-cooled, and pelletized, polypropylene-based cable material is obtained.

[0058] 3. Testing

[0059] The performance of each sample was tested, and the results are shown in Table 2.

[0060] Table 2: Aging and Electrical Performance Test Results of Each Sample

[0061]

[0062] Note: Oxidation induction period was tested according to GB 19466.6-2009 standard at a test temperature of 200℃. Dielectric strength was tested according to GB / T1408.1-2016 standard using symmetrical electrodes with an electrode diameter of 25mm and a test piece thickness of 1.0±0.1mm. Relative permittivity was tested according to GB / T 31838.6-2021 standard at a test piece thickness of 1.0±0.1mm. Volume resistivity was tested according to GB / T31838.2-2019 standard at a test temperature of 20℃ and a value of 1.0±0.1mm.

[0063] As shown in Table 2, sample 0#, which uses antioxidant B215, exhibits a very short oxidation induction period and poor anti-aging performance. Sample 1#, which does not contain hindered amine compounds or metal passivators, also has a very short oxidation induction period and poor anti-aging performance. Samples 2#-3#, also without hindered amine compounds, have relatively short oxidation induction periods and poor anti-aging performance. Sample 4#, which does not contain metal passivators, has an improved oxidation induction period compared to samples 0#-3#, but it is still relatively short, resulting in less than ideal anti-aging performance. However, the oxidation induction periods of Examples 1-5 (samples 5#-8#) of this invention are significantly extended while maintaining electrical performance that meets the requirements of insulated cables. This demonstrates that the combined effect of various components is necessary to effectively improve the anti-aging properties of the product and maintain good electrical performance.

[0064] 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 polypropylene-based cable material, characterized in that, The following steps are involved: The polypropylene-based cable base material and additive composition are premixed, then fed into a twin-screw extruder for shearing and extrusion, followed by stranding, air cooling and pelletizing to obtain the polypropylene-based cable material. The additive composition comprises, by weight percentage, the following components: The hindered phenolic compound is at least one selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; The hindered amine compound is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944 and light stabilizer 2020; The phosphite compound is at least one of tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol diphosphite (2,4-di-tert-butylphenol); The amount of the additive composition used is less than 0.5% of the mass of the polypropylene-based cable base material.

2. The preparation method according to claim 1, characterized in that, The metal passivating agent is BASF MD1024.

3. The preparation method according to claim 1, characterized in that, The lubricant is at least one of calcium stearate, zinc stearate, and magnesium stearate.

4. A polypropylene-based cable, characterized in that, The polypropylene-based cable material is prepared by the preparation method according to any one of claims 1 to 3.

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