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

Abstract

The invention provides an additive composition for a polypropylene-based material, a polypropylene-based cable material and a preparation method thereof, and a polypropylene-based cable. According to the additive composition for the polypropylene-based material, the specific hindered phenol compound, the hindered amine compound, the phosphite ester compound, the metal deactivator and the lubricant are matched according to a certain proportion, and the components act together and cooperate with one another, so that the polypropylene macromolecular chain is protected; compared with the prior art, the additive composition has the advantages that the degradation phenomenon of a polypropylene molecular chain in the presence of oxygen and light is reduced, the anti-aging performance of the polypropylene-based cable material is remarkably improved, the oxidation induction period of the polypropylene-based cable material at 200 DEG C is prolonged by more than 3 times, meanwhile, the additive composition has small influence on the polypropylene-based cable material, and the index requirement of the electrical performance of an insulated cable is met. In addition, during actual use, the additive composition is low in dosage, and the cost can be effectively reduced.

Description

Technical Field

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

[0002] Polypropylene (PP)-based thermoplastic insulation materials have the advantages of no need for cross-linking, no introduction of cross-linking by-products, and can be melted and reused. They also have excellent insulation and heat resistance comparable to cross-linked polyethylene. They are recognized as environmentally friendly cable insulation materials that can replace cross-linked polyethylene and are the main insulation materials for high-voltage DC cables. Compared with traditional XLPE (cross-linked polyethylene), PP has stronger insulation properties, better thermal stability, relatively low prices and simpler production processes. Polypropylene production does not require cross-linking and degassing, and is environmentally friendly and degradable, which is conducive to carbon reduction and emission reduction, recycling and reuse. It has unique advantages in simplifying production processes, shortening production cycles, reducing costs, and increasing production rates.

[0003] During use, polyolefin materials are affected by oxygen in the air and ultraviolet rays in the sun, which causes thermal oxidation or photooxidation of polyolefin materials, causing the physical and mechanical properties of polyolefin products to deteriorate, and lose their original functions and use value prematurely. The oxidation induction period (OIT) is a relative measure of the material's resistance to oxidative decomposition, and can be used to evaluate the material's own stabilization level.

[0004] Antioxidants and light stabilizers added to plastic materials can effectively inhibit or reduce the thermal oxidative aging and photooxidative aging rates 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] In the research of polypropylene-based insulating cable materials, the focus is mainly on improving the rigidity, poor toughness and poor low-temperature impact resistance of polypropylene itself through chemical copolymerization modification or material blending modification, so as to meet the mechanical property requirements of high-voltage DC cable insulation. The stabilizer combination currently used is B215, but there are problems such as large addition amount and high cost, and the effect of improving the anti-aging performance of polypropylene is not good. 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 and a preparation method thereof, and a polypropylene-based cable. The additive composition for polypropylene-based materials provided by the present invention can effectively improve the anti-aging performance of the polypropylene-based cable material while ensuring its electrical performance, and its dosage is small and the cost is low.

[0007] The present invention provides an additive composition for polypropylene-based materials, which comprises the following components by mass percentage:

[0008]

[0009] Preferably, the hindered phenol compound is at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, n-octadecylβ-(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 bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite.

[0012] Preferably, the metal passivator is BASF MD1024.

[0013] Preferably, the lubricant is at least one of 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, the additive used in 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 the additive composition are premixed, and then sent into a twin-screw extruder for shearing and extrusion, and then subjected to strip drawing, air cooling and pelletizing to obtain a polypropylene-based cable material;

[0018] Wherein, the additive composition is the additive composition for polypropylene-based materials 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 the present invention is obtained by combining specific hindered phenol compounds, hindered amine compounds, phosphite compounds, metal passivators and lubricants in a certain proportion. The above components work together and cooperate with each other to protect the polypropylene macromolecular chain, reduce the degradation of the polypropylene molecular chain in the presence of oxygen and light, and significantly improve the anti-aging performance of polypropylene-based cable materials. The oxidation induction period of polypropylene-based cable materials at 200°C is increased by more than 3 times. At the same time, the additive composition has little effect on polypropylene-based cable materials, meeting the index requirements of the electrical performance of insulating cables. In addition, when the above additive composition is actually used, its dosage is less than 0.5% of the mass of the polypropylene-based material, and the dosage is low, which can effectively reduce costs. DETAILED DESCRIPTION

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0022] In this article, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0023] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0024] Herein, when it comes to numerical ranges, unless otherwise specified, the numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0025] In this article, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left and right endpoints are the same. For example, 150-280℃ means that the units of the left endpoint "150" and the right endpoint "280" are both ℃.

[0026] Only some numerical ranges are specifically disclosed herein. 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, and likewise any upper limit can be combined with any other upper limit to form an unspecified range. In addition, each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unspecified range.

[0027] The present invention provides an additive composition for polypropylene-based materials, which comprises the following components by mass percentage:

[0028]

[0029] In the present invention, the hindered phenol compound is preferably at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (i.e. antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl ester (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). The above antioxidants can be derived from BASF. In the present invention, the amount of the hindered phenol compound is 10% to 40%, specifically 10%, 15%, 19.6%, 20%, 25%, 30%, 35%, 39.2%, 40%.

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

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

[0032] In the present invention, the metal passivator is preferably BASF MD1024. In the present invention, the amount of the metal passivator is 1% to 5%, specifically 1%, 2%, 3%, 4%, 5%.

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

[0034] In the present invention, the dosage of the above components is preferably 100%.

[0035] In one embodiment of the present invention, the additive composition is as follows:

[0036]

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

[0038]

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

[0040]

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

[0042]

[0043] In the present invention, when the additive composition for polypropylene-based materials is actually used, its usage is preferably less than 0.5% of the mass of the polypropylene-based material, and more preferably 0.2% to 0.4%, which is a relatively low usage.

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

[0045] The additive composition for polypropylene-based materials provided by the present invention is obtained by combining specific hindered phenol compounds, hindered amine compounds, phosphite compounds, metal passivators and lubricants in a certain proportion. The above components work together and cooperate with each other to protect the polypropylene macromolecular chain, reduce the degradation of the polypropylene molecular chain in the presence of oxygen and light, and significantly improve the anti-aging performance of polypropylene-based cable materials. The oxidation induction period of polypropylene-based cable materials at 200°C is increased by more than 3 times. At the same time, the additive composition has little effect on polypropylene-based cable materials, meeting the index requirements of the electrical performance of insulating cables. In addition, when the above additive composition is actually used, its dosage is less than 0.5% of the mass of the polypropylene-based material, and the dosage is low, which can effectively reduce costs.

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

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

[0048] In the present invention, the polypropylene-based cable base material is not particularly limited, and can be a conventional polypropylene-based cable base material in the art. In the present invention, the premixing can be carried out in a mixer, specifically in a high-speed mixer. The above various materials are mixed by premixing. The mixed material is fed into a twin-screw extruder by a feeder, and the material is sheared and blended by the twin-screw extruder and then extruded from the die, and then drawn, air-cooled, and pelletized to obtain a polypropylene-based cable material. In the present invention, the temperature of each section of the screw of the twin-screw extruder is preferably controlled at 150 to 280°C. The feeding frequency is preferably 5 to 45Hz, specifically 5Hz, 10Hz, 15Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, and 45Hz. The speed of the twin-screw main engine is preferably 60-150 rpm, specifically 60 rpm, 70 rpm, 80 rpm, 90 rpm, 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, 150 rpm. After the above preparation process, a master batch, i.e., a 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] In order 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, rather than limiting the claims of the present invention.

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

[0052] 1. Raw materials

[0053] The additive composition formulas of Comparative Examples 1-5 and Examples 1-4 correspond to samples 0# to 8# in Table 1. The units of the amounts of the components in the table are parts by mass.

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

[0055]

[0056] 2. Preparation

[0057] The polypropylene-based cable base material (i.e., polypropylene) and the additive composition are premixed in a high-speed mixer in proportion. The mixed materials are fed into a twin-screw extruder by a feeder, and the materials are sheared and blended by the twin-screw extruder, extruded from the die, and then stretched, air-cooled, and pelletized to obtain a polypropylene-based cable material.

[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: The oxidation induction period is tested according to GB 19466.6-2009 standard, and the measuring temperature is 200℃. The dielectric strength is tested according to GB / T1408.1-2016 standard, using symmetrical electrodes, the electrode diameter is 25mm, and the test piece thickness is 1.0±0.1mm. The relative dielectric constant is tested according to GB / T 31838.6-2021 standard, and the test piece thickness is 1.0±0.1mm. The volume resistivity is tested according to GB / T31838.2-2019 standard, 1.0±0.1mm, and the test temperature is 20℃.

[0063] It can be seen from the test results in Table 2 that sample 0# uses antioxidant B215. It can be seen that the oxidation induction period of this sample is very short and the anti-aging performance is poor. Sample 1# does not add hindered amine compounds and metal passivators. As a result, the oxidation induction period of this sample is also very short and the anti-aging performance is poor. Samples 2#-3# do not add hindered amine compounds. As a result, the oxidation induction period of the samples is also short and the anti-aging performance is poor. Sample 4# does not add metal passivators. Although its oxidation induction period is improved compared with samples 0#-3#, it is also relatively short and the anti-aging performance is not ideal. The oxidation induction period of Examples 1-5 of the present invention (i.e., samples 5#~8#) is significantly extended, while ensuring that the electrical performance meets the index requirements of the electrical performance of the insulated cable, proving that the present invention can effectively improve the anti-aging performance of the product and maintain good electrical performance under the joint cooperation of various components.

[0064] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. An additive composition for polypropylene-based materials, characterized in that: In terms of mass percentage, it includes the following components:

2. The additive composition according to claim 1, characterized in that The hindered phenol compound is at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 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.

3. The additive composition according to claim 1, characterized in that The hindered amine compound is at least one of light stabilizer 770, light stabilizer 622, light stabilizer 944 and light stabilizer 2020.

4. The additive composition according to claim 1, characterized in that The phosphite compound is at least one of tris(2,4-di-tert-butylphenyl)phosphite and bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite.

5. The additive composition according to claim 1, characterized in that The metal passivator is BASF MD1024.

6. The additive composition according to claim 1, characterized in that The lubricant is at least one of calcium stearate, zinc stearate and magnesium stearate.

7. The additive composition according to claim 1, characterized in that The polypropylene-based material is a polypropylene-based cable material.

8. A polypropylene-based cable material, characterized in that: The additive used is the additive composition for polypropylene-based materials described in any one of claims 1 to 7.

9. A method for preparing a polypropylene-based cable material according to claim 8, characterized in that: The following steps are involved: The polypropylene-based cable base material and the additive composition are premixed, and then sent into a twin-screw extruder for shearing and extrusion, and then subjected to strip drawing, air cooling and pelletizing to obtain a polypropylene-based cable material; Wherein, the additive composition is the additive composition for polypropylene-based materials according to any one of claims 1 to 7.

10. A polypropylene-based cable, characterized in that: Made from the polypropylene-based cable material described in claim 9.

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