CN111471236A - A kind of polypropylene cable insulating material and its preparation method and use - Google Patents
A kind of polypropylene cable insulating material and its preparation method and use Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 94
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011810 insulating material Substances 0.000 title abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 239000012774 insulation material Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000007872 degassing Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000006698 induction Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical class C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 241000143437 Aciculosporium take Species 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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Abstract
本发明公开了一种聚丙烯电缆绝缘材料及其制备方法、用途。所述聚丙烯复合绝缘材料的质量分数100％计，包括99.5‑99.9％的聚丙烯基体和0.1‑0.5％的硫代双酚类化合物填料。其中所述的硫代双酚类化合物包括受阻酚单元和含硫单元，受阻酚单元通过质子转移捕获基体中产生的自由基，含硫单元高效分解氢过氧化物使之成为无害的产物。本发明所制备的高热氧稳定性的聚丙烯电缆绝缘材料具有氧化诱导期长，直流击穿强度高，不易积聚空间电荷等特点，适用于高压直流电缆中。
The invention discloses a polypropylene cable insulating material, a preparation method and an application thereof. The mass fraction of the polypropylene composite insulating material is 100%, including 99.5-99.9% of polypropylene matrix and 0.1-0.5% of thiobisphenol compound filler. The thiobisphenol compound includes a hindered phenol unit and a sulfur-containing unit, the hindered phenol unit captures the free radicals generated in the matrix through proton transfer, and the sulfur-containing unit efficiently decomposes the hydroperoxide to make it into a harmless product. The polypropylene cable insulating material with high thermal-oxygen stability prepared by the invention has the characteristics of long oxidation induction period, high DC breakdown strength, and is not easy to accumulate space charge, and is suitable for high-voltage DC cables.
Description
技术领域technical field
本发明属于电气电子材料制备技术领域，具体涉及一种聚丙烯电缆绝缘材料及其制备方法、用途。The invention belongs to the technical field of preparation of electrical and electronic materials, and particularly relates to a polypropylene cable insulating material, a preparation method and uses thereof.
背景技术Background technique
聚丙烯是一种环保型高压直流电缆绝缘材料，相比于传统的交联聚乙烯绝缘料，具有工作温度高，电导率低，击穿强度高，不易积聚空间电荷等优势。但聚丙烯材料在热、氧气、光等作用下易发生老化，降低击穿场强，缩短使用寿命。因此，需要在聚丙烯材料中添加抗氧剂。Polypropylene is an environmentally friendly high-voltage DC cable insulation material. Compared with traditional cross-linked polyethylene insulation materials, it has the advantages of high working temperature, low electrical conductivity, high breakdown strength, and not easy to accumulate space charges. However, polypropylene materials are prone to aging under the action of heat, oxygen, light, etc., which reduces the breakdown field strength and shortens the service life. Therefore, it is necessary to add antioxidants to polypropylene materials.
当前面临的问题是：一方面，当抗氧剂添加量较低时，抗氧化效率较低，增加电缆使用寿命作用不明显；当抗氧剂添加量较高时，大幅降低电缆的电气性能。另一方面，不同类型的抗氧剂抗氧化机理和效率不同，对聚丙烯电气性能的影响机理和能力也不同。因此，在甄选适用于聚丙烯电线电缆的抗氧剂时，需要兼顾提高抗氧化能力和保持优良电气性能两方面。硫代双酚类化合物不仅兼具自由基捕获和氢过氧化物分解双重功能，在击穿过程中抑制低密度区形成，最终提高聚丙烯的击穿性能，而且分子量较低，极大提高抗氧化效率。The current problems are: on the one hand, when the amount of antioxidant added is low, the antioxidant efficiency is low, and the effect of increasing the service life of the cable is not obvious; when the amount of antioxidant added is high, the electrical performance of the cable is greatly reduced. On the other hand, different types of antioxidants have different antioxidant mechanisms and efficiencies, as well as different influence mechanisms and abilities on the electrical properties of polypropylene. Therefore, when selecting antioxidants suitable for polypropylene wires and cables, it is necessary to take into account both the improvement of antioxidant capacity and the maintenance of excellent electrical properties. Thiobisphenol compounds not only have the dual functions of free radical trapping and hydroperoxide decomposition, but also inhibit the formation of low-density regions during the breakdown process, and ultimately improve the breakdown performance of polypropylene. Oxidation efficiency.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于在保证高压直流电缆用聚丙烯优良电气性能的前提下，提高其抗热氧老化性能，为此提供一种聚丙烯电缆绝缘材料及其制备方法、用途。在等规聚丙烯中添加硫代双酚类抗氧剂，其中的受阻酚单元通过质子转移捕获基体中产生的自由基，抑制过氧自由基生成氢过氧化物，并且抑制聚丙烯材料内部低密度区的形成，最终增大材料的击穿强度；含硫单元高效分解氢过氧化物使之成为无害的产物，从而显著提升聚丙烯的使用寿命。The purpose of the present invention is to improve the thermal-oxidative aging resistance of polypropylene for high-voltage direct current cables on the premise of ensuring its excellent electrical properties, and to provide a polypropylene cable insulating material and a preparation method and uses thereof. Adding thiobisphenol antioxidants to isotactic polypropylene, the hindered phenol unit captures the free radicals generated in the matrix through proton transfer, inhibits the generation of hydroperoxide by peroxy radicals, and inhibits the internal low temperature of the polypropylene material. The formation of the density zone finally increases the breakdown strength of the material; the sulfur-containing unit efficiently decomposes the hydroperoxide into a harmless product, thereby significantly improving the service life of polypropylene.
本发明的第一个目的是提供一种聚丙烯电缆绝缘材料，所述聚丙烯复合绝缘材料的质量分数100％计，包括99.5-99.9％的聚丙烯基体和0.1-0.5％的硫代双酚化合物填料。The first object of the present invention is to provide a polypropylene cable insulation material, the mass fraction of the polypropylene composite insulation material is 100%, including 99.5-99.9% of polypropylene matrix and 0.1-0.5% of thiobisphenol Compound filler.
所述的聚丙烯基体为等规聚丙烯。The polypropylene matrix is isotactic polypropylene.
所述的抗氧剂为硫代双酚类化合物4,4'-硫代双(6-叔丁基-3-甲基苯酚)和4,4'-硫代双-(2-甲基-6-特丁基酚)中的一种或两种。The antioxidants are thiobisphenol compounds 4,4'-thiobis(6-tert-butyl-3-methylphenol) and 4,4'-thiobis-(2-methyl- 6-tert-butylphenol) one or both.
本发明的第二个目的是提供聚丙烯电缆绝缘材料制备方法，所述的制备方法如下步骤：The second object of the present invention is to provide a preparation method of polypropylene cable insulating material, and the preparation method is as follows:
A、将等规聚丙烯颗粒在双辊机上混炼10分钟使之充分熔融，温度设定为200℃；A. The isotactic polypropylene particles are mixed on a twin-roller for 10 minutes to fully melt, and the temperature is set to 200°C;
B、暂停混炼，将抗氧剂粉末与聚丙烯混合，使抗氧剂在等规聚丙烯内充分熔化；B. Pause the mixing, mix the antioxidant powder with the polypropylene, and make the antioxidant fully melt in the isotactic polypropylene;
C、将混合物在双辊机上继续充分混炼15分钟，温度设定为200℃，之后切割为若干份，每份1-2g；C. Continue to fully knead the mixture for 15 minutes on a twin-roller, set the temperature to 200°C, and then cut it into several parts, each 1-2g;
D、将混合材料脱气，冷却，在压片机上热压成型。D. Degas the mixed material, cool it, and heat it on a tablet press.
本发明所述的热压具体如下步骤：The hot pressing of the present invention is as follows:
A、取一份混合材料置于模具中，模具直径为70mm，深度为70/250μm；A. Take a portion of the mixed material and place it in a mold with a diameter of 70mm and a depth of 70/250μm;
B、将混合材料在压片机中热压15分钟，温度设定为200℃，压强设定为20MPa；B. The mixed material was hot-pressed in a tablet press for 15 minutes, the temperature was set to 200°C, and the pressure was set to 20MPa;
C、打开循环水箱，在1分钟内将压片机温度从200℃骤冷至80℃，取出。C. Open the circulating water tank, quench the temperature of the tablet press from 200°C to 80°C within 1 minute, and take it out.
本发明第三个目的是提供一种聚丙烯电缆绝缘材料用途，提高聚丙烯电缆绝缘材料高热氧稳定性。The third object of the present invention is to provide a use of polypropylene cable insulation material to improve the high thermo-oxidative stability of the polypropylene cable insulation material.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、选择硫代双酚类化合物作为填料，其中的受阻酚单元通过质子转移捕获基体中产生的自由基，抑制过氧自由基生成氢过氧化物，并且抑制聚丙烯材料内部低密度区的形成，最终增大材料的击穿强度；含硫单元高效分解氢过氧化物使之成为无害的产物，从而显著提升聚丙烯的使用寿命。1. Select thiobisphenol compounds as fillers, in which the hindered phenol unit captures the free radicals generated in the matrix through proton transfer, inhibits the generation of hydroperoxide by peroxy radicals, and inhibits the formation of low-density areas inside the polypropylene material , and finally increase the breakdown strength of the material; the sulfur-containing unit efficiently decomposes the hydroperoxide to make it a harmless product, thereby significantly improving the service life of polypropylene.
2、选择硫代双酚类化合物作为填料，其分子量为358，抗氧化效率较高；熔点与等规聚丙烯接近，提高了填料与基体的相容性。2. The thiobisphenol compound is selected as the filler, its molecular weight is 358, and the anti-oxidation efficiency is high; the melting point is close to that of isotactic polypropylene, which improves the compatibility between the filler and the matrix.
2、经30-90℃下的直流击穿强度测试，本发明制备的高热氧稳定性的聚丙烯电缆绝缘材料具有较高的直流击穿强度，适用于高压直流电缆。2. According to the DC breakdown strength test at 30-90 DEG C, the polypropylene cable insulating material with high thermo-oxidative stability prepared by the present invention has high DC breakdown strength and is suitable for high-voltage DC cables.
3、经210℃下的氧化诱导期测试，本发明制备的高热氧稳定性的聚丙烯电缆绝缘材料具备较高的氧化诱导期，适用于高压直流电缆。3. After the oxidation induction period test at 210° C., the polypropylene cable insulating material with high thermal and oxygen stability prepared by the present invention has a relatively high oxidation induction period, and is suitable for high-voltage direct current cables.
附图说明Description of drawings
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其他特征、目的和优点将会变得更明显：Other features, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments with reference to the following drawings:
图1为本发明所述等规聚丙烯(a)、两种硫代双酚类化合物：4,4'-硫代双(6-叔丁基-3-甲基苯酚)(b)和4,4'-硫代双-(2-甲基-6-特丁基酚)的分子式(c)；Fig. 1 is the isotactic polypropylene (a) of the present invention, two thiobisphenol compounds: 4,4'-thiobis(6-tert-butyl-3-methylphenol) (b) and 4 , the molecular formula (c) of 4'-thiobis-(2-methyl-6-tert-butylphenol);
图2为实施例1所制备的聚合物复合材料的氧化诱导时间；Fig. 2 is the oxidation induction time of the polymer composite material prepared in Example 1;
图3为实施例1所制备的聚合物复合材料在30-90℃下的直流击穿强度。3 is the DC breakdown strength of the polymer composite prepared in Example 1 at 30-90°C.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明的实验测试样品在差示扫描量热仪中测量氧化诱导期。Experimental test samples of the present invention were measured for oxidative induction period in a differential scanning calorimeter.
本发明的实验测试样品在由试验变压器、调压器、阻抗分压器和示波器等组成的击穿强度测试平台测量直流击穿强度。The experimental test sample of the present invention measures the DC breakdown strength on a breakdown strength test platform composed of a test transformer, a voltage regulator, an impedance voltage divider and an oscilloscope.
本发明提供了一种提高聚丙烯电缆绝缘材料高热氧稳定性的方法。所述聚丙烯复合绝缘材料的质量分数100％计，包括99.5-99.9％的聚丙烯基体和0.1-0.5％的硫代双酚类化合物填料。The invention provides a method for improving the high thermal-oxygen stability of polypropylene cable insulation materials. The mass fraction of the polypropylene composite insulating material is 100%, including 99.5-99.9% of polypropylene matrix and 0.1-0.5% of thiobisphenol compound filler.
所述的聚丙烯基体为等规聚丙烯，其作为环保型高压直流电缆绝缘材料具有工作温度高，击穿强度大，不易积聚空间电荷，易于回收等优点。The polypropylene matrix is isotactic polypropylene, which as an environment-friendly HVDC cable insulation material has the advantages of high working temperature, high breakdown strength, not easy to accumulate space charge, easy to recycle, and the like.
优选地，所述的抗氧剂为硫代双酚类化合物4,4'-硫代双(6-叔丁基-3-甲基苯酚)和4,4′-硫代双-(2-甲基-6-特丁基酚)中的一种或两种。此两种硫代双酚类化合物分子量均为358，所含官能团相同，抗氧化效率较高。Preferably, the antioxidants are thiobisphenol compounds 4,4'-thiobis(6-tert-butyl-3-methylphenol) and 4,4'-thiobis-(2- one or both of methyl-6-tert-butylphenol). Both of the two thiobisphenol compounds have a molecular weight of 358, contain the same functional groups, and have high antioxidant efficiency.
本发明提供了高热氧稳定性聚丙烯电缆绝缘材料的制备方法，所述方法包括如下步骤：The present invention provides a method for preparing a polypropylene cable insulating material with high thermal and oxygen stability. The method comprises the following steps:
A、将等规聚丙烯颗粒在双辊机上混炼10分钟使之充分熔融，温度设定为200℃；A. The isotactic polypropylene particles are mixed on a twin-roller for 10 minutes to fully melt, and the temperature is set to 200°C;
B、暂停混炼，将抗氧剂粉末与聚丙烯混合，使抗氧剂在等规聚丙烯内充分熔化；B. Pause the mixing, mix the antioxidant powder with the polypropylene, and make the antioxidant fully melt in the isotactic polypropylene;
C、将混合物在双辊机上继续充分混炼15分钟，温度设定为200℃，之后切割为若干份，每份1-2g；C. Continue to fully knead the mixture for 15 minutes on a twin-roller, set the temperature to 200°C, and then cut it into several parts, each 1-2g;
D、将混合材料脱气，冷却，在压片机上热压成型D. Degas the mixed material, cool it, and heat it on a tablet press
优选地，步骤C中所述的热压方法如下步骤：Preferably, the hot pressing method described in step C is as follows:
A、取一份混合材料置于模具中，模具直径为70mm，深度为70/250μm；A. Take a portion of the mixed material and place it in a mold with a diameter of 70mm and a depth of 70/250μm;
B、将混合材料在压片机中热压15分钟，温度设定为200℃，压强设定为20MPa；B. The mixed material was hot-pressed in a tablet press for 15 minutes, the temperature was set to 200°C, and the pressure was set to 20MPa;
C、打开循环水箱，在1分钟内将压片机温度从200℃骤冷至80℃，取出。C. Open the circulating water tank, quench the temperature of the tablet press from 200°C to 80°C within 1 minute, and take it out.
本发明采用兼具捕获自由基和分解氢氧化物功能的硫代双酚类化合物作为填料，以电气性能优异的等规聚丙烯作为基体，通过熔融共混法制备出具有高热氧稳定性同时绝缘性能优异的高压直流电缆用聚丙烯绝缘料。The present invention adopts the thiobisphenol compound with the functions of capturing free radicals and decomposing hydroxide as filler, and using isotactic polypropylene with excellent electrical properties as the matrix, and prepares a product with high thermal-oxygen stability and insulation through a melt blending method. Polypropylene insulation material for high-voltage DC cables with excellent performance.
实施例1Example 1
本实施例涉及一种高热氧稳定性的聚丙烯电缆绝缘材料，所述聚丙烯复合绝缘材料的质量分数100％计，包括99.7％的聚丙烯基体和0.3％的硫代双酚化合物填料。其中高热氧稳定性的聚丙烯电缆绝缘材料的制备方法如下步骤：This embodiment relates to a polypropylene cable insulation material with high thermal and oxygen stability. The polypropylene composite insulation material includes 99.7% polypropylene matrix and 0.3% thiobisphenol compound filler based on 100% mass fraction. Wherein the preparation method of the polypropylene cable insulating material with high thermo-oxidative stability is as follows:
A、将29.91g等规聚丙烯颗粒在双辊机上混炼10分钟使之充分熔融，温度设定为200℃；A. Mix 29.91g of isotactic polypropylene particles on a twin-roller for 10 minutes to fully melt them, and set the temperature to 200°C;
B、暂停混炼，将0.09g 4,4'-硫代双(6-叔丁基-3-甲基苯酚)和4,4'-硫代双-(2-甲基-6-特丁基酚)分别与等规聚丙烯混合，使其在等规聚丙烯内充分熔化；B. Suspend mixing, mix 0.09g of 4,4'-thiobis(6-tert-butyl-3-methylphenol) and 4,4'-thiobis-(2-methyl-6-tert-butylene) base phenol) were mixed with isotactic polypropylene to make it fully melted in isotactic polypropylene;
C、将混合物在双辊机上继续充分混炼15分钟，温度设定为200℃，之后切割为若干份，每份1-2g；C. Continue to fully knead the mixture for 15 minutes on a twin-roller, set the temperature to 200°C, and then cut it into several parts, each 1-2g;
D、将混合材料脱气，冷却，在压片机中热压15分钟，温度设定为200℃，压强设定为20MPa；打开循环水箱，在1分钟内将压片机温度从200℃骤冷至80℃，取出。D. Degas the mixed material, cool it, press it in the tablet press for 15 minutes, set the temperature to 200°C, and set the pressure to 20MPa; open the circulating water tank, and change the temperature of the tablet press from 200°C to 200°C within 1 minute. Cool to 80°C and remove.
实施例2Example 2
本实施例涉及一种高热氧稳定性的聚丙烯电缆绝缘材料，所述聚丙烯复合绝缘材料的质量分数100％计，包括99.5％的聚丙烯基体和0.5％的硫代双酚化合物填料。其他步骤同实施例1。This embodiment relates to a polypropylene cable insulation material with high thermal and oxygen stability, and the mass fraction of the polypropylene composite insulation material is 100%, including 99.5% polypropylene matrix and 0.5% thiobisphenol compound filler. Other steps are the same as in Example 1.
实施例3Example 3
本实施例涉及一种高热氧稳定性的聚丙烯电缆绝缘材料，所述聚丙烯复合绝缘材料的质量分数100％计，包括99.9％的聚丙烯基体和0.1％的硫代双酚化合物填料。其他步骤同实施例1。This embodiment relates to a polypropylene cable insulating material with high thermal and oxygen stability. The polypropylene composite insulating material, in terms of mass fraction of 100%, includes 99.9% polypropylene matrix and 0.1% thiobisphenol compound filler. Other steps are the same as in Example 1.
对比例1Comparative Example 1
本对比例涉及一种高热氧稳定性的聚丙烯电缆绝缘材料，所述聚丙烯复合绝缘材料的质量分数100％计，包括99.5％的聚丙烯基体和0.5％的硫代双酚化合物填料。其中高热氧稳定性的聚丙烯电缆绝缘材料的制备方法同实施例1。This comparative example relates to a polypropylene cable insulating material with high thermal and oxygen stability. The polypropylene composite insulating material comprises 99.5% polypropylene matrix and 0.5% thiobisphenol compound filler based on 100% mass fraction. The preparation method of the polypropylene cable insulating material with high thermal oxygen stability is the same as that in Example 1.
综上所述，本发明通过在等规聚丙烯中添加两种硫代双酚类化合物，其中的受阻酚单元通过质子转移捕获基体中产生的自由基，抑制过氧自由基生成氢过氧化物，并且抑制聚丙烯材料内部低密度区的形成，最终增大材料的击穿强度；含硫单元高效分解氢过氧化物使之成为无害的产物，从而显著提升聚丙烯的使用寿命。制备出的高热氧稳定性的聚丙烯电缆绝缘材料不仅具有较高的氧化诱导期，并且其直流击穿强度也得到明显提升。To sum up, in the present invention, two kinds of thiobisphenol compounds are added to isotactic polypropylene, wherein the hindered phenol unit captures the free radicals generated in the matrix through proton transfer, and inhibits the generation of hydroperoxide by peroxy radicals. , and inhibit the formation of low-density areas inside the polypropylene material, and finally increase the breakdown strength of the material; the sulfur-containing unit efficiently decomposes the hydroperoxide to make it a harmless product, thereby significantly improving the service life of polypropylene. The prepared polypropylene cable insulation material with high thermo-oxidative stability not only has a higher oxidation induction period, but also has a significantly improved DC breakdown strength.
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