CN114292466A - Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof - Google Patents
Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof Download PDFInfo
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Abstract
A modified polypropylene insulating material for medium and low voltage power cables is mainly prepared from the following raw materials in parts by weight: 60-95 parts of polypropylene resin; 5-40 parts of a thermoplastic elastomer; 5-10 parts of modified grafting material; 0.5-3 parts of nano oxide; the thermoplastic elastomer is one or more of ethylene-octene copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer; the modified grafting material is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer and methacrylate grafted polypropylene; the nano oxide is silane coupling agent modified nano alumina and/or nano magnesia. The invention adopts three modes of elastomer blending modification, nano modification and grafting modification at the same time, and introduces the thermoplastic elastomer, the grafting material and the nano oxide as the polypropylene modifier, so that the performance of the polypropylene is obviously improved, and the polypropylene modifier is more suitable for the use requirement of a cable insulating layer.
Description
Technical Field
The invention belongs to the field of power cable insulating materials, and particularly relates to a modified polypropylene insulating material for a medium-low voltage power cable and a preparation method thereof.
Background
Since 1980, the crosslinked polyethylene insulated cable is widely applied to power distribution networks, industrial devices or other fields requiring large-capacity power utilization, and is fixedly laid on power transmission and distribution lines with 50Hz alternating current and 6-500 kV rated voltage. However, the production of the medium-high voltage crosslinked polyethylene power cable has the disadvantages of large energy consumption, complex processing technology, non-recyclability and the like, so that the development of the power cable is limited, and the defects are specifically shown as follows:
(1) the crosslinked polyethylene material cannot be recycled, and does not accord with the concept of green economy;
(2) the crosslinking and degassing process required by the polyethylene material enables the production time and cost of the cable to be increased dramatically, which is far higher than that of a thermoplastic insulated cable, and the production time of the crosslinked polyethylene cable is about 5-10 times of that of the thermoplastic insulated cable.
(3) Dicumylperoxide (DCP) is one of the most commonly used crosslinkers in the production of crosslinked polyethylene, but the cumyl alcohol [ (CH) is produced after crosslinking3)2CHC6H4CH2OH]Polar byproducts such as acetophenone and the like can increase the dielectric constant of the product, so that the capacitance of the alternating current cable is increased, and the power transmission loss is increased; this is also an important source of space charge generation and accumulation at dc voltages, which severely affects the lifetime of dc cables.
(4) The cross-linked polyethylene cable has insulation hidden troubles such as 'water tree' and the like during operation; the definition of water tree in DL/T1070-2007 is "micro-channels developed in the presence of moisture, electrical stress and some inducing factors such as impurities, protrusions, space charge or ions in insulation", and water tree is a phenomenon in which polymer insulation material is degraded under the action of alternating electric field and moisture. Under the combined action of moisture and an electric field, water trees are the main cause of damage to high-voltage power cables, and can bring adverse factors to urban power supply reliability with abundant underground water and high cable coverage rate.
Therefore, new process materials are always searched for to replace crosslinked polyethylene in the cable industry at home and abroad. Since the 21 st century, developed countries such as europe and japan have turned research and development to polypropylene (PP) insulated power cables, polypropylene has the characteristics of excellent insulating property, high temperature resistance level, recycling and the like, and when used as an insulating material for power cables, the polypropylene has great advantages in improving current-carrying capacity, and also far surpasses crosslinked polyethylene in the aspects of simplifying processing technology, reducing cost, increasing production rate, greatly improving cable length and the like, and simultaneously has excellent water tree resistance compared with crosslinked polyethylene.
Since the research on the polypropylene insulating material is only carried out for over ten years, most of medium and low voltage insulated cables on the market are still crosslinked polyethylene insulated cables at present, and the polypropylene insulated cables do not replace the polyethylene insulated cables on a large scale and are multi-angle, on one hand, the research time is short, the performance of the polypropylene insulating material on the market cannot meet the increasing market standard, on the other hand, the specific reason is that a mature polypropylene insulating material product does not appear, and the application of the existing polypropylene insulated cables is limited because the low temperature resistance and the electric performance are poor.
Disclosure of Invention
The invention provides a modified polypropylene insulating material for medium and low voltage power cables and a preparation method thereof, and aims to solve the problem that the low temperature resistance and the electrical performance of the existing polypropylene insulating material cannot meet the market requirements.
In order to achieve the purpose, the invention adopts the technical scheme that:
the modified polypropylene insulating material for the medium and low voltage power cable is characterized in that: the material is mainly prepared from the following raw materials in parts by weight:
60-95 parts of polypropylene resin;
5-40 parts of a thermoplastic elastomer;
5-10 parts of modified grafting material;
0.5-3 parts of nano oxide;
the thermoplastic elastomer is one or a mixture of at least two of ethylene-octene copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer;
the modified grafting material is one or a mixture of at least two of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer and methacrylate grafted polypropylene;
the nano oxide is silane coupling agent modified nano alumina and/or nano magnesia.
Preferably, the polypropylene resin is isotactic polypropylene, the isotacticity is not less than 95 percent, the melt index is 2.0-7.0g/10min, and the flexural modulus is 500-1000kg/cm2。
Preferably, the hydrogenated styrene-butadiene block copolymer has a viscosity of 2.0 to 3.0 and a styrene content of 25 to 33%.
Preferably, the grafting rate of the modified grafting material is 0.6-1.0%.
Preferably, the silane coupling agent is vinyl tri (b-methoxyethoxy) silane, and the particle size of the nano oxide is 50-100 nm.
Preferably, the polypropylene insulating material further comprises 1-4 parts of antioxidant, wherein the antioxidant is composed of a main antioxidant and an auxiliary antioxidant, the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-3: 1, the main antioxidant is at least one of antioxidant 1010, antioxidant 1035 and antioxidant 1024, and the auxiliary antioxidant is phosphite antioxidant and/or thiobisphenol antioxidant.
Preferably, the phosphite antioxidant comprises at least one of antioxidant 168, antioxidant 626 and antioxidant TNPP; the thiobisphenol antioxidant comprises at least one of antioxidant DLTP and antioxidant DSTP.
The technical scheme of the invention also provides a preparation method for preparing the insulating material, which is characterized by sequentially comprising the following steps of: weighing the thermoplastic elastomer and the nano oxide according to a weight ratio, and stirring and mixing the thermoplastic elastomer and the nano oxide at the speed of 400-500 rpm for 3-5 min at room temperature to obtain a first mixture; putting the first mixture into a double-screw extruder, performing melt extrusion, cooling, granulating and drying to obtain a master batch; weighing the polypropylene resin and the modified grafting material according to a weight ratio, and stirring the polypropylene resin and the modified grafting material together with the master batch at room temperature at a speed of 400-500 rpm for 3-5 min to obtain a second mixture; and putting the second mixture into an extruder of a reciprocating machine, and performing melt extrusion, cooling, granulation and drying to obtain the modified polypropylene insulating material for the medium and low voltage power cable.
Preferably, the extrusion temperature of the twin-screw extruder and the reciprocating extruder is set to 140 ℃ and 190 ℃.
Preferably, the antioxidant, the polypropylene resin and the modified grafting material are respectively weighed according to a weight ratio, and then are stirred together with the master batch at room temperature at a speed of 400-500 rpm for 3-5 min, so as to obtain a second mixture.
The design principle and the effect of the invention are as follows:
1. through the addition of the thermoplastic elastomer, the grafting material and the nano oxide, the low-temperature resistance and the electrical performance of the polypropylene material are improved, the insulating material which can be applied to the insulating layer of the medium and low voltage power cable is obtained, and the requirements of crosslinked polyethylene (XLPE) in the national standard GB/T12706 of the medium and low voltage power cable are met;
the addition of the thermoplastic elastomer effectively reduces the flexural modulus of the material and increases the low-temperature resistance of the material; the modified grafting material mainly uses maleic anhydride grafted materials (maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer and methacrylate grafted polypropylene), and the maleic anhydride grafted materials are beneficial to introducing deep traps into the structure, inhibiting space charges, keeping higher thermal stability and also having better mechanical property and insulating property after the insulating material is aged; the silane coupling agent modified nano oxide has a large amount of organic groups on the surface, so that the surface energy of the nano oxide is reduced, the affinity between the nano oxide and polypropylene molecules is improved, physical mixing is facilitated on one hand, and an interface region is formed between the nano oxide and the polypropylene on the other hand, so that a deep trap is introduced into a structure, and the electrical performance is indirectly improved.
2. The invention adopts three modes of elastomer blending modification, nano modification and grafting modification at the same time, and introduces the thermoplastic elastomer, the grafting material and the nano oxide as the polypropylene modifier, so that the performance of the polypropylene is obviously improved, and the polypropylene modifier is more suitable for the use requirement of a cable insulating layer. Due to the introduction of the thermoplastic elastomer, the flexural modulus of the material is reduced, and the low-temperature resistance is improved; the introduction of the grafting material obviously improves the electrical performance of the material and simultaneously adjusts the mechanical performance and the thermal performance; the introduction of the nano oxide improves the electrical performance of the material, and the breakdown field strength is obviously improved; by combining the three modification modes, the low-temperature resistance and the electrical performance of the polypropylene material are improved simultaneously in an all-around and multi-angle manner so as to reach multiple national standards, and the polypropylene material is applied to insulating layers of medium and low voltage power cables.
3. In the technical scheme, the antioxidant is also limited, and is compounded by a main oxidant and an auxiliary oxidant, wherein the main oxidant adopts conventional antioxidant 1010, antioxidant 1035 and antioxidant 1024, and the auxiliary oxidant adopts phosphite antioxidant and/or thiobisphenol antioxidant (belonging to hindered phenol antioxidant); the phosphite antioxidant can effectively decompose hydroperoxide (the generation and accumulation of the hydroperoxide are the most critical steps for degrading organic high molecular materials, and after the hydroperoxide with a certain concentration is generated, the free radical oxidation reaction is rapidly promoted), so that the phosphite antioxidant has good color protection capability, can improve the processing temperature of polymers, and has a good synergistic effect with the hindered phenol antioxidant.
Detailed Description
The invention is further described below in connection with examples 1-9:
example (b):
table one: EXAMPLES 1-5 insulation compositions
Table two: EXAMPLES 6-9 insulation compositions
Table three: examples 1-5 Performance List:
table four: examples 6-9 Performance List:
the nano-alumina and the nano-magnesia in the above embodiments are both the silane coupling agent modified nano-alumina or nano-magnesia.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The modified polypropylene insulating material for the medium and low voltage power cable is characterized in that: the material is mainly prepared from the following raw materials in parts by weight:
60-95 parts of polypropylene resin;
5-40 parts of a thermoplastic elastomer;
5-10 parts of modified grafting material;
0.5-3 parts of nano oxide;
the thermoplastic elastomer is one or a mixture of at least two of ethylene-octene copolymer, hydrogenated styrene-butadiene block copolymer and ethylene propylene diene monomer;
the modified grafting material is one or a mixture of at least two of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer and methacrylate grafted polypropylene;
the nano oxide is silane coupling agent modified nano alumina and/or nano magnesia.
2. The insulation material according to claim 1, characterized in that: the polypropylene resin is isotactic polypropylene, the isotacticity is more than or equal to 95 percent, the melt index is 2.0-7.0g/10min, and the flexural modulus is 500-1000kg/cm2。
3. The insulation material according to claim 1, characterized in that: the hydrogenated styrene-butadiene block copolymer has a viscosity of 2.0 to 3.0 and a styrene content of 25 to 33%.
4. The insulation material according to claim 1, characterized in that: the grafting rate of the modified grafting material is 0.6-1.0%.
5. The insulation material according to claim 1, characterized in that: the silane coupling agent is vinyl tri (b-methoxyethoxy) silane, and the particle size of the nano oxide is 50-100 nm.
6. The insulation material according to claim 1, characterized in that: the polypropylene insulating material further comprises 1-4 parts of antioxidant, wherein the antioxidant is composed of a main antioxidant and an auxiliary antioxidant, the mass ratio of the main antioxidant to the auxiliary antioxidant is 1: 1-3: 1, the main antioxidant is at least one of antioxidant 1010, antioxidant 1035 and antioxidant 1024, and the auxiliary antioxidant is phosphite antioxidant and/or thiobisphenol antioxidant.
7. The insulation material according to claim 6, characterized in that: the phosphite antioxidant comprises at least one of antioxidant 168, antioxidant 626 and antioxidant TNPP; the thiobisphenol antioxidant comprises at least one of antioxidant DLTP, antioxidant DSTP and antioxidant 300.
8. A preparation method for the insulating material as claimed in any one of claims 1 to 7, characterized by sequentially comprising the following steps: weighing the thermoplastic elastomer and the nano oxide according to a weight ratio, and stirring and mixing the thermoplastic elastomer and the nano oxide at the speed of 400-500 rpm for 3-5 min at room temperature to obtain a first mixture; putting the first mixture into a double-screw extruder, performing melt extrusion, cooling, granulating and drying to obtain a master batch; weighing the polypropylene resin and the modified grafting material according to a weight ratio, and stirring the polypropylene resin and the modified grafting material together with the master batch at room temperature at a speed of 400-500 rpm for 3-5 min to obtain a second mixture; and putting the second mixture into an extruder of a reciprocating machine, and performing melt extrusion, cooling, granulation and drying to obtain the modified polypropylene insulating material for the medium and low voltage power cable.
9. The method of claim 8, wherein: the extrusion temperature of the twin-screw extruder and the reciprocating extruder was set at 140 ℃ and 190 ℃.
10. The method of claim 8, wherein: and respectively weighing the antioxidant, the polypropylene resin and the modified grafting material according to a weight ratio, and stirring the antioxidant, the polypropylene resin and the modified grafting material together with the master batch at room temperature at a speed of 400-500 rpm for 3-5 min to obtain a second mixture.
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| CN202111484620.3A CN114292466A (en) | 2021-12-07 | 2021-12-07 | Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof |
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| CN202111484620.3A CN114292466A (en) | 2021-12-07 | 2021-12-07 | Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof |
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| CN115850870A (en) * | 2023-03-02 | 2023-03-28 | 南京中超新材料股份有限公司 | Polypropylene modified insulating material and preparation method thereof |
| CN116199978A (en) * | 2023-02-21 | 2023-06-02 | 上海至正新材料有限公司 | Low-shrinkage thermoplastic polypropylene insulating material for medium-voltage cable and preparation method thereof |
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