CN110003505B - Modification method of polypropylene-based insulating material for high-voltage direct-current cable - Google Patents
Modification method of polypropylene-based insulating material for high-voltage direct-current cable Download PDFInfo
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- CN110003505B CN110003505B CN201910144430.3A CN201910144430A CN110003505B CN 110003505 B CN110003505 B CN 110003505B CN 201910144430 A CN201910144430 A CN 201910144430A CN 110003505 B CN110003505 B CN 110003505B
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Abstract
The invention discloses a modification method of a polypropylene-based insulating material for a high-voltage direct-current cable, which comprises the steps of fully mixing and reacting a polypropylene composite base material, an organic solvent and a crosslinking agent in a reaction kettle with pressure resistance, heating and stirring functions to obtain a nano-modified polypropylene-based composite insulating material. Firstly, adding a polypropylene composite base material and an organic solvent into a reaction kettle; opening a heating device to heat and maintain the polypropylene composite base material and the organic solvent in the reaction kettle; stirring; adding a cross-linking agent accounting for 1-3% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 5-10 min, and stopping stirring and heating the reaction kettle; and (5) cooling and recycling. The organic solvent has low toxicity, can be produced in a closed way, can be recycled and has excellent economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of high-voltage direct-current transmission equipment, and particularly relates to a modification method of a polypropylene-based high-voltage cable insulating material.
Background
In recent years, high-voltage power transmission technology has been spotlighted, and high-voltage direct-current cables are used as key equipment of direct-current power transmission technology, and have important strategic significance in the aspects of island power transmission, ocean resource development and utilization, urban power grid transformation and upgrading, distributed energy grid-connected power transmission and the like. The cross-linked polyethylene cable widely used at present has the working temperature of only 70 ℃ and can not be recycled after the working life is reached. In recent years, recyclable polypropylene-based cable insulation materials are widely concerned by researchers and cable manufacturers at home and abroad. The polypropylene material not only has excellent dielectric property, but also has higher melting point, and development and application of the two properties are beneficial to improving the running temperature, voltage and line current-carrying capacity of the polypropylene cable, and the application prospect is huge.
Under the high-voltage direct-current electric field, on one hand, the injection and accumulation of space charges in the cable polymer insulating material can cause the distortion of a local electric field, accelerate insulation aging and reduce dielectric strength in an insulating medium, and can cause insulation breakdown fault in severe cases. On the other hand, the current passing through the cable at a high voltage level is large, and the heat generated by the wire core enables the cable to operate at a higher temperature for a long time, so that the conductivity of the insulating material at a high temperature becomes large, and the injection, migration and insulation ageing of space charges are further aggravated. Therefore, the space charge characteristic of the insulating material is improved, and the method has important significance for safe operation and high-capacity power transmission of the high-voltage direct-current cable.
In recent years, nano materials are rapidly developed, and the size effect and interface effect of the nano materials have a great influence on the performance of the nano composite materials. At present, a method for improving the space charge characteristic of a polypropylene insulating material is mostly adopted to directly carry out simple mechanical blending modification on nano particles and a polypropylene matrix material. However, due to the characteristics of easy agglomeration and difficult uniform dispersion of the nano particles, the defects of large feeding amount and insufficient mixing exist in the actual industrial production, and the space charge performance of the polypropylene nano composite insulating material is more easily degraded. Therefore, how to improve the dispersibility and interface compatibility of the nano particles in the polypropylene matrix material and further improve the space charge characteristic of the polypropylene-based insulating material for the high-voltage direct-current cable has important application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modification method of a polypropylene-based insulating material for a high-voltage direct-current cable.
The invention adopts the technical scheme that the polypropylene composite base material, the organic solvent and the cross-linking agent are fully mixed and reacted in a reaction kettle with pressure resistance, heating and stirring functions to obtain the nano modified polypropylene-based composite insulating material. The invention relates to a modification method of a polypropylene-based insulating material for a high-voltage direct-current cable, which comprises the following steps of fully mixing and reacting a polypropylene composite base material, an organic solvent and a crosslinking agent in a reaction kettle with pressure resistance, heating and stirring functions to obtain a nano-modified polypropylene-based composite insulating material:
(1) Feeding: firstly, adding a polypropylene composite base material and an organic solvent into a reaction kettle;
the polypropylene composite base material is formed by mixing polypropylene, octavinyl POSS and an antioxidant, wherein the mass ratio of the polypropylene to the octavinyl POSS is 4:1-5:1, and the antioxidant accounts for 1% -5% of the total mass of the polypropylene and the octavinyl POSS;
(2) Heating: opening a heating device to heat and maintain the polypropylene composite base material and the organic solvent in the reaction kettle;
the temperature rise is 5-10 ℃ lower than the boiling point of the organic solvent;
(3) Stirring: opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant and maintained;
(4) Grafting reaction: adding a cross-linking agent accounting for 1-3% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 5-10 min, and stopping stirring and heating the reaction kettle;
(5) And (3) cooling and recycling: after the temperature in the reaction kettle is reduced, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining pure organic solvent and modified polypropylene-based composite insulating material;
the temperature reduction temperature is 20-30 ℃ lower than the boiling point of the organic solvent.
The polypropylene in the step (1) comprises isotactic polypropylene, syndiotactic polypropylene or a blend of the isotactic polypropylene and syndiotactic polypropylene;
octavinyl-POSS with CAS number 69655-76-1 and molecular equation C16H24O12Si8;
antioxidants, including antioxidant 1010, antioxidant 1076, antioxidant 618, antioxidant 626, antioxidant 300, antioxidant 1035, and mixtures thereof.
The organic solvent in the step (2) comprises toluene (CAS number 108-88-3, molecular formula C7H 8), xylene (CAS number 1330-20-7, molecular formula C8H 10), isoamyl acetate (CAS number 123-92-2, molecular formula C7H14O 2), decalin (CAS number 91-17-8, chemical formula C10H 18) and the input volume ratio (calculated by L) is 5-6 times of the mass (calculated by kg) of the polypropylene composite base material.
The stirring speed in the step (3) is set to be 30-50r/min.
The cross-linking agent in the step (4) comprises dicumyl peroxide (chemical formula is C18H22O2, CAS number is 80-43-3), dibenzoyl peroxide (molecular formula is C14H10O4, CAS number is 94-36-0) and vulcanizing agent double 25 (molecular formula is C16H34O4, CAS number is 78-63-7).
Compared with the prior art, the invention has the following advantages:
(1) The nano particles can be uniformly dispersed in the polypropylene-based composite insulating material, the interfacial compatibility between the nano particles and polypropylene is better, and the insulating material for the high-voltage direct-current cable with excellent performance can be prepared.
(2) The organic solvent has low toxicity, can be produced in a closed way, can be recycled and has excellent economic and environmental benefits.
(3) The process equipment is easy to realize, the flow is clear and easy to control, the dangerousness of parameters such as temperature, rotating speed, air pressure and the like in the production process is low, and the operability and the realizability are excellent.
Drawings
FIG. 1 is a flow chart of a method for modifying a polypropylene-based insulating material for a high-voltage direct-current cable;
fig. 2 shows a polypropylene-based insulating material modifying apparatus for a high-voltage direct-current cable.
The drawing shows that the device comprises a 1-computer control unit, a 2-liner, a 3-sealing cover, a 4-heating control unit, a 5-resistance heating wire, a 6-thermocouple sensor, a 7-heat-resistant insulating layer, an 8-motor control and driving unit, a 9-motor, a 10-stirring rod, a 11-condensation control unit, a 12-circulating pump, a 13-refrigerator, a 14-heat conducting oil, a 15-condensing pipe, a 16-recovery tank, a 17-vacuum pump and a 18-waste gas treatment tank.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
Firstly, polypropylene (Henan petrochemical, PPH-T03), octavinyl POSS (Zhengzhou alpha chemical Co., ltd.) and antioxidant 1010 (Germany BASF Basoff) are mixed according to the mass ratio of 80:20:1 is put into a reaction kettle, and a dimethylbenzene organic solvent with the volume ratio (calculated by L) accounting for 5 times of the mass (calculated by Kg) of the polypropylene composite base material is put into the reaction kettle. And (3) turning on a heating device to heat the polypropylene composite base material and the organic solvent in the reaction kettle to 125 ℃ and keeping the temperature. And (3) opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant at 30r/min and maintained. Adding dicumyl oxide as a crosslinking agent accounting for 1% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 5min, and stopping stirring and heating. After the temperature in the reaction kettle is reduced to 110 ℃, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining the pure organic solvent and the modified polypropylene-based composite insulating material.
Example 2
Firstly, polypropylene (Henan petrochemical, PPH-T03), octavinyl POSS (Zhengzhou alpha chemical Co., ltd.) and an antioxidant 1076 (Germany BASF Basoff) are mixed according to the mass ratio of 90:16:2, putting the mixture into a reaction kettle, and putting toluene which is an organic solvent and occupies 5.5 times of the mass (Kg) of the polypropylene composite base material in volume proportion (L) into the reaction kettle. And (3) turning on a heating device to heat the polypropylene composite base material and the organic solvent in the reaction kettle to 100 ℃ and keeping the temperature. And (3) opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant at 35r/min and maintained. Adding dicumyl oxide as a crosslinking agent accounting for 1.5% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 5min, and stopping stirring and heating the device. After the temperature in the reaction kettle is reduced to 90 ℃, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining the pure organic solvent and the modified polypropylene-based composite insulating material.
Example 3
Firstly, polypropylene (Hainan petrochemical industry, PPH-T03), octavinyl POSS (Zhengzhou alpha chemical Co., ltd.), an antioxidant 1010 (Germany BASF Basoff) and an antioxidant 618 (Germany BASF Basoff) are mixed according to a mass ratio of 80:20:1.5:1.5 is put into a reaction kettle, and an isoamyl acetate organic solvent with the volume ratio (calculated as L) accounting for 6 times of the mass (calculated as Kg) of the polypropylene composite base material is put into the reaction kettle. And (3) turning on a heating device to heat the polypropylene composite base material and the organic solvent in the reaction kettle to 130 ℃ and keeping. And (3) opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant at 30r/min and maintained. And (3) adding dibenzoyl peroxide serving as a cross-linking agent accounting for 3% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 6min, and stopping stirring and heating. After the temperature in the reaction kettle is reduced to 120 ℃, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining the pure organic solvent and the modified polypropylene-based composite insulating material.
Example 4
Firstly, polypropylene (Hainan petrochemical industry, PPH-T03), octavinyl POSS (Zhengzhou alpha chemical Co., ltd.), an antioxidant 626 (Germany BASF Basoff) and an antioxidant 1035 (Germany BASF Basoff) are mixed according to a mass ratio of 90:16:2.5:2.5 is put into a reaction kettle, and an isoamyl acetate organic solvent with a volume ratio (calculated as L) which is 5 times of the mass (calculated as Kg) of the polypropylene composite base material is put into the reaction kettle. And (3) turning on a heating device to heat the polypropylene composite base material and the organic solvent in the reaction kettle to 130 ℃ and keeping. And (3) opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant at 30r/min and maintained. And (3) adding dibenzoyl peroxide serving as a cross-linking agent accounting for 3% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 6min, and stopping stirring and heating. After the temperature in the reaction kettle is reduced to 120 ℃, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining the pure organic solvent and the modified polypropylene-based composite insulating material.
Example 5
Firstly, polypropylene (Henan petrochemical, PPH-T03), octavinyl POSS (Zhengzhou alpha chemical Co., ltd.) and an antioxidant 300 (Germany BASF Basoff) are mixed according to the mass ratio of 80:20:5, putting the mixture into a reaction kettle, and putting decalin organic solvent with the volume ratio (calculated by L) accounting for 6 times of the mass (calculated by Kg) of the polypropylene composite base material into the reaction kettle. And (3) turning on a heating device to heat the polypropylene composite base material and the organic solvent in the reaction kettle to 175 ℃ and keeping. And (3) opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant at 30r/min and maintained. Adding cross-linking agent vulcanizing agent double 25 accounting for 2% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 6min, and stopping stirring and heating the device. After the temperature in the reaction kettle is reduced to 160 ℃, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining the pure organic solvent and the modified polypropylene-based composite insulating material.
The process flow of the present invention is shown in figure 1.
As shown in figure 2, the invention adopts a set of polypropylene-based insulating material modification device for high-voltage direct-current cables, and the device consists of a computer control unit, a reaction kettle, a heating device, a stirring device and a suction filtration recovery device.
The computer control unit 1 has a man-machine interaction interface function and a communication function; wherein the man-machine interaction interface function can set material parameters, heating temperature, stirring speed, vacuum filtration air pressure, condensation temperature and the like); the communication function can send instructions to the heating device, the stirring device and the suction filtration recovery device, so as to control the process flow.
The reaction kettle consists of a cylindrical stainless steel inner container 2 and a stainless steel sealing cover 3, and has the performances of vacuum tightness and atmospheric pressure resistance of 10 MPa.
The heating device comprises a heating control unit 4, a thermocouple sensor 6, a resistance heating wire 5 and a heat-resistant insulating layer 7, wherein the heating control unit can receive a temperature control instruction issued by the computer control unit 1, temperature feedback information of the thermocouple sensor 6 and control power on-off of the resistance heating wire 5, the thermocouple sensor 6 is positioned in a reaction kettle, and the resistance heating wire 5 uniformly surrounds the outside of the reaction kettle and is coated by the heat-resistant insulating layer.
Wherein the stirring device consists of a motor control and driving unit 8, a motor 9 and a stirring rod 10; wherein, the motor control and driving unit 8 can receive the rotating speed control instruction issued by the computer control unit 1 to drive the motor 9, and the stirring rod 10 passes through the stainless steel sealing cover 3 of the reaction kettle.
The suction filtration recovery device consists of a condensation unit, a vacuum pump 17, a recovery tank 16 and an exhaust gas treatment tank 18; the condensing unit consists of a condensing control unit 11, a refrigerator 13, heat conducting oil 14, a circulating 12 pump and a condensing pipe 15, and forms a closed loop; wherein the exhaust treatment tank 18 contains activated carbon and has an opening; wherein, reation kettle, condensing unit, recovery jar, vacuum pump, exhaust-gas treatment jar link to each other in proper order through stainless steel hollow tube.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. A modification method of a polypropylene-based insulating material for a high-voltage direct-current cable is characterized in that polypropylene composite base material, organic solvent and cross-linking agent are fully mixed and reacted in a reaction kettle with pressure resistance, heating and stirring functions to obtain a nano modified polypropylene-based composite insulating material, and the method specifically comprises the following steps:
(1) Feeding: firstly, adding a polypropylene composite base material and an organic solvent into a reaction kettle;
the polypropylene composite base material is formed by mixing polypropylene, octavinyl POSS and an antioxidant, wherein the mass ratio of the polypropylene to the octavinyl POSS is 4:1-5:1, and the antioxidant accounts for 1% -5% of the total mass of the polypropylene and the octavinyl POSS;
(2) Heating: opening a heating device to heat and maintain the polypropylene composite base material and the organic solvent in the reaction kettle;
the temperature rise is 5-10 ℃ lower than the boiling point of the organic solvent;
(3) Stirring: opening a stirring device to enable the polypropylene composite base material in the reaction kettle to be fully dissolved in the organic solvent, wherein the stirring speed is constant and maintained;
(4) Grafting reaction: adding a cross-linking agent accounting for 1-3% of the total mass of the polypropylene and the octavinyl POSS into a reaction kettle, stirring for 5-10 min, and stopping stirring and heating the reaction kettle;
(5) And (3) cooling and recycling: after the temperature in the reaction kettle is reduced, opening a suction filtration recovery device to perform suction filtration, gasification and condensation recovery on the organic solvent in the reaction kettle, and respectively obtaining pure organic solvent and modified polypropylene-based composite insulating material;
the temperature reduction temperature is 20-30 ℃ lower than the boiling point of the organic solvent.
2. The method for modifying a polypropylene-based insulating material for a high voltage direct current cable according to claim 1, wherein the polypropylene in the step (1) comprises isotactic polypropylene, syndiotactic polypropylene or a blend of both;
octavinyl-POSS;
antioxidants, including antioxidant 1010, antioxidant 1076, antioxidant 618, antioxidant 626, antioxidant 300, antioxidant 1035, and mixtures thereof.
3. The method for modifying a polypropylene-based insulating material for a high voltage direct current cable according to claim 1, wherein the organic solvent in the step (2) comprises toluene, xylene, isoamyl acetate (CAS No. 123-92-2, molecular formula C 7 H 14 O 2 ) The added volume ratio of decalin is calculated by L, and is 5-6 times of the mass of the polypropylene composite base material calculated by kg.
4. The method for modifying a polypropylene-based insulating material for a high-voltage direct-current cable according to claim 1, wherein the stirring speed in the step (3) is set to 30-50r/min.
5. The method for modifying a polypropylene-based insulating material for a high voltage direct current cable according to claim 1, wherein the crosslinking agent in the step (4) comprises dicumyl peroxide, dibenzoyl peroxide and vulcanizing agent bis 25.
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| CN201910144430.3A CN110003505B (en) | 2019-02-27 | 2019-02-27 | Modification method of polypropylene-based insulating material for high-voltage direct-current cable |
| PCT/CN2019/080312 WO2020172942A1 (en) | 2019-02-27 | 2019-03-29 | Device and method for modifying polypropylene-based insulating material for high-voltage direct-current cable |
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| CN201910144430.3A CN110003505B (en) | 2019-02-27 | 2019-02-27 | Modification method of polypropylene-based insulating material for high-voltage direct-current cable |
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| CN112029218B (en) * | 2020-08-26 | 2022-08-12 | 哈尔滨理工大学 | POSS (polyhedral oligomeric silsesquioxane) grafted modified polypropylene high-voltage direct-current cable material and preparation method thereof |
| CN113845734B (en) * | 2021-10-22 | 2023-09-19 | 万华化学（宁波）有限公司 | Thermoplastic polypropylene cable insulating material for high voltage and preparation method thereof |
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| FR3026547B1 (en) * | 2014-09-26 | 2023-04-07 | Nexans | ELECTRICAL DEVICE COMPRISING A CROSS-LINKED LAYER |
| CN205517763U (en) * | 2016-04-21 | 2016-08-31 | 新疆华爱康塑业科技发展有限公司 | Polyethylene crosslinked preparation system |
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