CN110498997A - A kind of polypropylene-base high voltage direct current cable material and preparation method thereof - Google Patents
A kind of polypropylene-base high voltage direct current cable material and preparation method thereof Download PDFInfo
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- CN110498997A CN110498997A CN201910662131.9A CN201910662131A CN110498997A CN 110498997 A CN110498997 A CN 110498997A CN 201910662131 A CN201910662131 A CN 201910662131A CN 110498997 A CN110498997 A CN 110498997A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
A kind of polypropylene-base high voltage direct current cable material and preparation method thereof, according to the mass fraction, 10~50 parts of the isotactic polypropylene containing beta nucleater, 50~90 parts of ethylene-propylene block copolymer polypropylene and 0.10.5 parts of antioxidant；Wherein, the sum of the isotactic polypropylene containing beta nucleater and the mass fraction of ethylene-propylene block copolymer polypropylene are 100 parts, and the mass fraction of beta nucleater is 0.3%~1% in the isotactic polypropylene containing beta nucleater.The present invention passes through being blended for EPC and β-iPP by using the co-blend polypropylene material that addition beta nucleater and the method that is blended with block polypropylene of isotactic polypropylene prepare the crystal containing β, it is big to solve isotactic polypropylene brittleness, the low problem of the dielectric breakdown strength of low-temperature impact difference and EPC, provides the polypropylene-base direct current high voltage cable material of the good alternative XLPE of green recyclable mechanics, electric property simultaneously a kind of.
Description
Technical field
The present invention relates to thermoplasticity direct current cables Material Field, especially a kind of polypropylene-base high voltage direct current cable material and its
Preparation method.
Background technique
XLPE has excellent mechanical performance and electric property, is the predominating insulation of extrusion pressing type plastic cable.But
Due to the by-product that cross-linking process generates, the space charge accumulation of direct current cables is produced bigger effect.The accumulation of space charge
It will lead to cable insulation internal electric field to be distorted, so as to cause the shelf depreciation and breakdown of cable insulation, reduce the exhausted of material
Edge performance.In addition, crosslinked polyethylene is thermosetting material, it can not degrade and recycle after cable is retired, burning can only be passed through
And landfill disposal, environment is caused greatly to pollute.Therefore the thermoplastic cable material that urgent need is met environmental requirements
Research and development are to replace crosslinked polyethylene.Polypropylene not only has good electric property and a heat resistance, but also as thermoplastic material,
It can be recycled after end-of-life, it is possible to instead of crosslinked polyethylene as cable material.However, isotactic polypropylene brittleness
Very big, low temperature impact properties are poor, these disadvantages limit it in the use of high voltage direct current cable.Researcher's choosing both domestic and external
Blending, copolymerization, the brittleness and cryogenic property for changing the methods of crystal form and chemical modification improvement isotactic polypropylene are taken.
Summary of the invention
The purpose of the present invention is to provide a kind of polypropylene-base high voltage direct current cable material and preparation method thereof, this method preparations
High-voltage DC cable insulating material, have excellent mechanical performance and electric property.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of polypropylene-base high voltage direct current cable material, according to the mass fraction, the isotactic polypropylene 10~50 containing beta nucleater
Part, 50~90 parts of ethylene-propylene block copolymer polypropylene and 0.1~0.5 part of antioxidant；Wherein, the isotactic containing beta nucleater is poly-
The sum of mass fraction of propylene and ethylene-propylene block copolymer polypropylene is 100 parts, in the isotactic polypropylene containing beta nucleater β at
The mass fraction of core agent is 0.3%~1%.
A further improvement of the present invention lies in that the isotactic polypropylene containing beta nucleater is made by following procedure:
1) it prepares the polypropylene masterbatch containing beta nucleater: isotactic polypropylene, beta nucleater being added in twin screw compounder and melted
Melt blending, is squeezed out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Wherein, the quality of beta nucleater
It is 5%~10% of the polypropylene masterbatch quality containing beta nucleater；
2) it prepares semi-finished product material: the polypropylene masterbatch containing beta nucleater being added in twin screw compounder with polypropylene and is melted
It is blended, is squeezed out after mixing through twin-screw, obtain the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater is accounted for containing beta nucleater
Isotactic polypropylene mass percent be 0.3%~1%.
A further improvement of the present invention lies in that the melt index of isotactic polypropylene is 2.9 ± 0.2g/10min.
A further improvement of the present invention lies in that beta nucleater 2,6- cyclohexanedimethanol amide, N, dicyclohexyl -2 N ' -,
One or both of 6- naphthalene diamides, TMB-4, TMB-5, rare earth nucleating agent WBG-II.
A further improvement of the present invention lies in that the mass fraction of ethylene segment is in ethylene-propylene block copolymer polypropylene
10%~20%, the melt index of ethylene-propylene block copolymer polypropylene is 2.1 ± 0.2g/10min.
A further improvement of the present invention lies in that antioxidant was four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons
Doutrate, three (2.4- di-tert-butyl-phenyl) phosphite esters, one in 4,4'- thiobis (6- tert-butyl -3- methylphenol)
Kind is several.
A further improvement of the present invention lies in that when antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid]
Pentaerythritol ester, three (2.4- di-tert-butyl-phenyl) phosphite esters, in 4,4'- thiobis (6- tert-butyl -3- methylphenol)
At two or three, the mass fraction that every kind of antioxidant accounts for antioxidant gross mass is no less than 10%.
A kind of preparation method of such as above-mentioned polypropylene-base high voltage direct current cable material, comprising the following steps:
1) it prepares the polypropylene masterbatch containing beta nucleater: isotactic polypropylene, beta nucleater being added in twin screw compounder and melted
Melt blending, is squeezed out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Wherein, the quality of beta nucleater
It is 5%~10% of the polypropylene masterbatch quality containing beta nucleater；
2) it prepares semi-finished product material: the polypropylene masterbatch containing beta nucleater being added in twin screw compounder with polypropylene and is melted
It is blended, is squeezed out after mixing through twin-screw, obtain the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater is accounted for containing beta nucleater
Isotactic polypropylene mass percent be 0.3%~1%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater, which are pressed, to be added
Enter in twin screw compounder, uniformly squeezes out and be sent into pelleter after cooling after pelletizing, obtain polypropylene-base high voltage direct current cable
Material.
A further improvement of the present invention lies in that the temperature in each area of screw rod is set as 195~200 DEG C, feed opening in step 1)
Revolving speed is 8~12rpm, and screw speed is 150~200rpm；
In step 2), the temperature in each area of screw rod is set as 195~200 DEG C, and feed opening revolving speed is 12~16rpm, and screw rod turns
Speed is 200~300rpm.
A further improvement of the present invention lies in that the temperature in each area of screw rod is set as 195~200 DEG C, feed opening in step 3)
Revolving speed is 12~16rpm, and screw speed is 200~300rpm
Compared with prior art, the invention has the following advantages: the present invention is by using addition beta nucleater and waits
The co-blend polypropylene material for method preparation crystal containing β that isotactic polypropylene is blended with block polypropylene, has excellent mechanical performance,
For mechanical stretch elongation at break up to 600% or more, tensile strength reaches 25MPa, and brittle temperature drops to -30 DEG C or less.Simultaneously
Electric property is good, and room temperature dc breakdown intensity reaches 200kV/mm, does not observe after application high field 50kV/mm polarization 30min bright
Aobvious space charge gathers.And it is environmental-friendly, green is recyclable.
For the present invention in preparation, while using blending and modifying and the method for adding beta nucleater, material has excellent machinery
Performance (room temperature impact property improve 15 times or more) and and electric property, environmental-friendly, thermoplastic material, the service life exhaust after can return
It receives, manufacturing process is without crosslinking, and simply and in use cross-linking agent-free by-product generates process.Thermoplastic poly third provided by the present invention
Alkenyl high voltage direct current cable material is a kind of breakthrough technical products, which is with ethylene-propylene block copolymer polypropylene
(EPC) be used as matrix resin, be blended with the isotactic polypropylene (iPP) containing nucleating agent, improve polyacrylic impact property,
The disadvantages of brittleness is big and ethylene-propylene block copolymer polypropylene breakdown strength is not high, due to being all using PP as matrix, crystalline state is one
Sample, the problem of not causing space charge to gather due to phase interface.The introducing of β crystal simultaneously can be further improved altogether
The mechanical property and electric property of mixed material.The CABLE MATERIALS has characteristics that thermoplasticity, environmental-friendly, and the service life exhausts rear easy
Recycling；Excellent mechanical performance and electric property etc., and there is good processing performance.
Detailed description of the invention
Fig. 1 is the metallographic microscope figure of iPP, EPC, EPC/iPP and EPC-iPP/ nucleating agent.Wherein, (a) is iPP, (b)
(c) it is EPC/iPP for EPC, (d) is EPC-iPP/ nucleating agent.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
A kind of high-pressure polypropylene base cable insulating material of the invention, it is according to the mass fraction, poly- including the isotactic containing nucleating agent
10~50 parts of propylene, 50~90 parts of ethylene-propylene block copolymer polypropylene and 0.1~0.5 part of antioxidant.Wherein, it is nucleated containing β
The sum of isotactic polypropylene and the mass fraction of ethylene-propylene block copolymer polypropylene of agent are 100 parts, and the isotactic containing beta nucleater is poly-
The mass fraction of beta nucleater is 0.3%~1% in propylene.
The melt index of isotactic polypropylene is that 2.9 ± 0.2g/10min (applies 2.16kg's at 230 ± 2 DEG C in the present invention
It is tested under active force).
Ethylene-propylene block copolymer polypropylene in the present invention, wherein the mass fraction of ethylene segment is 10%20%, melting
Index is 2.1 ± 0.2g/10min (applies at 230 ± 2 DEG C and test under the active force of 2.16kg).
The beta nucleater can induce polypropylene to generate β crystal in crystallization process, can be such as 2,6- phthalic acid ring
One of caproamide, N, N '-dicyclohexyl -2,6- naphthalene diamides, TMB-4, TMB-5, rare earth compound class WBG-II or two
Kind.
Antioxidant in the present invention is polypropylene antioxidant, the high temperature that can be resistant in process, such as four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2.4- di-tert-butyl-phenyl) phosphite esters, 4,4'- be thio
One or more of bis- (6- tert-butyl -3- methylphenols) are used cooperatively, when a variety of antioxygens are used cooperatively, every kind of antioxidant
The mass fraction of the total antioxidant of content Zhan be no less than 10%.
IPP brittleness is big, and low temperature impact properties are poor, and EPC dielectric strength is lower, cannot be directly used as cable material, it is necessary to right
It is modified.The present invention in EPC with β-iPP by being blended the low temperature impact properties for improving iPP, brittleness and Jie of EPC
Electric strength.The introducing of flower-shaped β crystal can improve the tensile property of intermingling material, dielectric strength, reduce gathering for space charge；
The addition of EPC can increase substantially the impact property and low temperature brittleness performance of intermingling material.
The preparation method of polypropylene-base high voltage direct current cable material of the invention is dispersed in guarantee that nucleating agent is uniform and stable
In polypropylene, finished product material is prepared using mother material and stepwise, specifically includes the following steps:
1) it prepares the polypropylene masterbatch containing beta nucleater: isotactic polypropylene (iPP), nucleating agent being proportionally added into miniature double
Melt blending in screw rod batch mixer, the temperature in each area of screw rod are set as (between 195~200 DEG C), feed opening revolving speed (8~
12rpm), screw speed (150~200rpm) is squeezed out after mixing by twin-screw and is obtained gathering containing 5%10% beta nucleater
Propylene masterbatch.
2) it prepares semi-finished product material: the polypropylene masterbatch containing 5%~10% beta nucleater being proportionally added into polypropylene miniature
Melt blending in twin screw compounder, the temperature in each area of screw rod are set as (between 195~200 DEG C), feed opening revolving speed (12~
16rpm), screw speed (200~300rpm) is squeezed out after mixing through twin-screw and is obtained containing 0.3%~1% beta nucleater
Semi-finished product material β-iPP.
3) finished product material is prepared: semi-finished product material β-iPP, ethylene-propylene block copolymerization poly- third containing 0.3%~1% beta nucleater
Alkene (EPC), antioxidant are proportionally added into twin screw compounder, and the temperature in each area of screw rod is set as (between 195~200 DEG C),
Feed opening revolving speed (12~16rpm), screw speed (200~300rpm) are uniformly squeezed out and are sent into pelleter after cooling treatment
The CABLE MATERIALS containing beta nucleater is obtained after pelletizing.In the CABLE MATERIALS, according to the mass fraction, including the isotactic polypropylene containing beta nucleater
10~50 parts, 50~90 parts of ethylene-propylene block copolymer polypropylene, 0.1~0.5 part of antioxidant.
Comparative example 1-2 of the present invention, embodiment 1-3, formula for raw stock are shown in Table 1.
1 thermoplastic polypropylene base cable insulation material formula of table
Wherein each embodiment is as follows:
Comparative example 1: according to the mass fraction, the ethylene-propylene block copolymer polypropylene Insulation Material produced using Yanshan Petrochemical
K8303 adds 0.1 part of antioxidant 1010.
Comparative example 2: according to the mass fraction, using the isotactic polypropylene T30s for extending petrochemical iy produced, irgasfos 168 is added
0.2 part.
Embodiment 1: according to the mass fraction, 70 parts of the ethylene-propylene block copolymer polypropylene of use, 30 parts of isotactic polypropylene,
0.1 part of antioxidant 300 of addition.
Embodiment 2: according to the mass fraction, 60 parts of the ethylene-propylene block copolymer polypropylene of use, 40 parts of isotactic polypropylene,
0.12 part of rare earth nucleating agent, add antioxidant 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester), irgasfos 168 (three (2.4- di-tert-butyl-phenyl) phosphite esters), antioxidant 300 (4,4 '-thiobis (6- tert-butyl -3-
Methylphenol)) it is respectively 0.1,0.2,0.1 part.
Embodiment 3: according to the mass fraction, 80 parts of the ethylene-propylene block copolymer polypropylene of use, 20 parts of isotactic polypropylene,
0.06 part of rare earth nucleating agent, add antioxidant 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester), irgasfos 168 (three (2.4- di-tert-butyl-phenyl) phosphite esters) be respectively 0.1,0.2 part.
3 kinds of cable preparation method for material of comparative example 1-2 in table 1, embodiment 1 are identical, by pellet after evenly mixing through miniature
(extruder temperature is 195~200 DEG C to double-screw melt blending extrusion, and screw speed is 200~300rpm, and feed opening revolving speed is 12
~16rpm).
The preparation method of 2 kinds of CABLE MATERIALSs of embodiment 23 is identical, comprises the following steps that:
1) it prepares the polypropylene masterbatch containing beta nucleater: isotactic polypropylene (iPP), nucleating agent being proportionally added into miniature double
Melt blending in screw rod batch mixer, the temperature in each area of screw rod are set as (between 195~200 DEG C), feed opening revolving speed (8~
12rpm), screw speed (150~200rpm) is squeezed out after mixing by twin-screw and is obtained containing 5%~10% beta nucleater
IPP masterbatch.
2) it prepares semi-finished product material: the iPP masterbatch containing 5%~10% beta nucleater is proportionally added into miniature double spiral shells with pure iPP
Melt blending in bar batch mixer, the temperature in each area of screw rod are set as (between 195~200 DEG C), feed opening revolving speed (12~
16rpm), screw speed (200~300rpm) is squeezed out after mixing through twin-screw and is obtained containing 0.3%~1% beta nucleater
Semi-finished product material β-iPP.
3) finished product material is prepared: semi-finished product material β-iPP, ethylene-propylene block copolymerization poly- third containing 0.3%~1% beta nucleater
Alkene (EPC), antioxidant are proportionally added into twin screw compounder, and the temperature in each area of screw rod is set as (between 195~200 DEG C),
Feed opening revolving speed (12~16rpm), screw speed (200~300rpm) are uniformly squeezed out and are sent into pelleter after cooling treatment
Obtain 10~50 parts of isotactic polypropylene containing beta nucleater after pelletizing, 50~90 parts of ethylene-propylene block copolymer polypropylene, antioxidant
0.1~0.5 part of CABLE MATERIALS.
The comprehensive performance of each embodiment CABLE MATERIALS is listed in table 2.
The comprehensive performance of the different embodiment CABLE MATERIALSs of table 2
As shown in FIG. 1, FIG. 1 is the crystal habit petrographic microscope figure of polypropylene-base Insulation Material, amplification factor is 400 times.
Fig. 1 (a) is the crystal petrographic microscope figure of iPP, and the α spherocrystal in iPP is in cross delustring, by center radial growth around,
Crystalline size is larger, and up to 200 μm or so, and between spherocrystal, there are apparent boundaries.Fig. 1 (b) is the crystal petrographic microscope of EPC
The α spherulite size generated in figure EPC is smaller, and more dense compared to iPP at 60 μm or so, the boundary between spherocrystal is unobvious.Figure
1 (c) is the crystal petrographic microscope figure of EPC/iPP, and the alpha-crystal size generated in EPC/iPP is at 100 μm or so, between spherocrystal
There is boundaries.Fig. 1 (d) is the crystal petrographic microscope figure of EPC/iPP- nucleating agent, and after adding nucleating agent, β crystalline substance is in flower-shaped life
Long, the size of β crystal is up to 300 μm or so.
Embodiment 4
1) polypropylene masterbatch containing beta nucleater is prepared: isotactic polypropylene, the β for being 2.9 ± 0.2g/10min by melt index
Melt blending in miniature twin screw compounder is added in nucleating agent, and the temperature in each area of screw rod is set as 195 DEG C, and feed opening revolving speed is
8rpm, screw speed 150rpm squeeze out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Its
In, the quality of beta nucleater is 10% of the polypropylene masterbatch quality containing beta nucleater；Beta nucleater is 2,6- cyclohexanedimethanol acyl
Amine.
2) semi-finished product material is prepared: will be in polypropylene masterbatch and the miniature twin screw compounder of polypropylene addition containing beta nucleater
Melt blending, the temperature in each area of screw rod are set as 200 DEG C, and feed opening revolving speed is 13rpm, screw speed 250rpm, through double spiral shells
Bar squeezes out after mixing, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater accounts for the isotactic poly- third containing beta nucleater
The mass percent of alkene is 1%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater, which are pressed, to be added
Enter in twin screw compounder, the temperature in each area of screw rod is set as 195 DEG C, and feed opening revolving speed is 12rpm, and screw speed is
200rpm uniformly squeezes out and is sent into pelleter after cooling after pelletizing, obtains polypropylene-base high voltage direct current cable material, the CABLE MATERIALS
In, according to the mass fraction, including 10 parts of isotactic polypropylene containing beta nucleater, 90 parts of ethylene-propylene block copolymer polypropylene, antioxygen
0.1 part of agent.The mass fraction of ethylene segment is 10% in ethylene-propylene block copolymer polypropylene, ethylene-propylene block copolymerization poly- third
The melt index of alkene is 2.1 ± 0.2g/10min.Antioxidant was four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol esters.
Embodiment 5
1) polypropylene masterbatch containing beta nucleater is prepared: isotactic polypropylene, the β for being 2.9 ± 0.2g/10min by melt index
Melt blending in miniature twin screw compounder is added in nucleating agent, and the temperature in each area of screw rod is set as 200 DEG C, and feed opening revolving speed is
12rpm, screw speed 170rpm squeeze out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Its
In, the quality of beta nucleater is 7% of the polypropylene masterbatch quality containing beta nucleater；Beta nucleater is 2,6- cyclohexanedimethanol acyl
Amine and N, the mixture of N '-dicyclohexyl -2,6- naphthalene diamides.
2) semi-finished product material is prepared: will be in polypropylene masterbatch and the miniature twin screw compounder of polypropylene addition containing beta nucleater
Melt blending, the temperature in each area of screw rod are set as 200 DEG C, and feed opening revolving speed is 14rpm, screw speed 220rpm, through double spiral shells
Bar squeezes out after mixing, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater accounts for the isotactic poly- third containing beta nucleater
The mass percent of alkene is 0.7%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater, which are pressed, to be added
Enter in twin screw compounder, the temperature in each area of screw rod is set as 197 DEG C, and feed opening revolving speed is 13rpm, and screw speed is
270rpm uniformly squeezes out and is sent into pelleter after cooling after pelletizing, obtains polypropylene-base high voltage direct current cable material, the CABLE MATERIALS
In, according to the mass fraction, including 50 parts of isotactic polypropylene containing beta nucleater, 50 parts of ethylene-propylene block copolymer polypropylene, antioxygen
0.2 part of agent.The mass fraction of ethylene segment is 15% in ethylene-propylene block copolymer polypropylene, ethylene-propylene block copolymerization poly- third
The melt index of alkene is 2.1 ± 0.2g/10min.Antioxidant is three (2.4- di-tert-butyl-phenyl) phosphite esters.
Embodiment 6
1) polypropylene masterbatch containing beta nucleater is prepared: isotactic polypropylene, the β for being 2.9 ± 0.2g/10min by melt index
Melt blending in miniature twin screw compounder is added in nucleating agent, and the temperature in each area of screw rod is set as 198 DEG C, and feed opening revolving speed is
10rpm, screw speed 180rpm squeeze out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Its
In, the quality of beta nucleater is 8% of the polypropylene masterbatch quality containing beta nucleater；Beta nucleater is the mixing of TMB-4 and TMB-5
Object.
2) semi-finished product material is prepared: will be in polypropylene masterbatch and the miniature twin screw compounder of polypropylene addition containing beta nucleater
Melt blending, the temperature in each area of screw rod are set as 195 DEG C, and feed opening revolving speed is 16rpm, screw speed 200rpm, through double spiral shells
Bar squeezes out after mixing, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater accounts for the isotactic poly- third containing beta nucleater
The mass percent of alkene is 20.5%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater, which are pressed, to be added
Enter in twin screw compounder, the temperature in each area of screw rod is set as 200 DEG C, and feed opening revolving speed is 16rpm, and screw speed is
240rpm uniformly squeezes out and is sent into pelleter after cooling after pelletizing, obtains polypropylene-base high voltage direct current cable material, the CABLE MATERIALS
In, according to the mass fraction, including 20 parts of isotactic polypropylene containing beta nucleater, 80 parts of ethylene-propylene block copolymer polypropylene, antioxygen
0.3 part of agent.The mass fraction of ethylene segment is 20% in ethylene-propylene block copolymer polypropylene, ethylene-propylene block copolymerization poly- third
The melt index of alkene is 2.1 ± 0.2g/10min.Antioxidant was four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
The mixture of four alcohol esters and three (2.4- di-tert-butyl-phenyl) phosphite esters, and four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester and three (2.4- di-tert-butyl-phenyl) phosphite ester mass ratioes are 1:9.
Embodiment 7
1) polypropylene masterbatch containing beta nucleater is prepared: isotactic polypropylene, the β for being 2.9 ± 0.2g/10min by melt index
Melt blending in miniature twin screw compounder is added in nucleating agent, and the temperature in each area of screw rod is set as 200 DEG C, and feed opening revolving speed is
11rpm, screw speed 200rpm squeeze out after mixing by twin-screw, obtain the polypropylene masterbatch containing beta nucleater；Its
In, the quality of beta nucleater is 5% of the polypropylene masterbatch quality containing beta nucleater；Beta nucleater is rare earth nucleating agent WBG-II.
2) semi-finished product material is prepared: will be in polypropylene masterbatch and the miniature twin screw compounder of polypropylene addition containing beta nucleater
Melt blending, the temperature in each area of screw rod are set as 195 DEG C, and feed opening revolving speed is 12rpm, screw speed 300rpm, through double spiral shells
Bar squeezes out after mixing, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater accounts for the isotactic poly- third containing beta nucleater
The mass percent of alkene is 1%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater, which are pressed, to be added
Enter in twin screw compounder, the temperature in each area of screw rod is set as 200 DEG C, and feed opening revolving speed is 14rpm, and screw speed is
300rpm uniformly squeezes out and is sent into pelleter after cooling after pelletizing, obtains polypropylene-base high voltage direct current cable material, the CABLE MATERIALS
In, according to the mass fraction, including 30 parts of isotactic polypropylene containing beta nucleater, 70 parts of ethylene-propylene block copolymer polypropylene, antioxygen
0.5 part of agent.The mass fraction of ethylene segment is 13% in ethylene-propylene block copolymer polypropylene, ethylene-propylene block copolymerization poly- third
The melt index of alkene is 2.1 ± 0.2g/10min.Antioxidant is three (2.4- di-tert-butyl-phenyl) phosphite esters and 4, and 4'- is thio
The mixture of bis- (6- tert-butyl -3- methylphenols), and three (2.4- di-tert-butyl-phenyl) phosphite esters and 4,4'- thiobis
The mass ratio of (6- tert-butyl -3- methylphenol) is 1:1.
The preparation method of the CABLE MATERIALS includes the preparation of cable material masterbatch, the works such as masterbatch and the melt blending of EPC, iPP
Skill step；Cable masterbatch is made of iPP, beta nucleater.Compared with prior art, the invention has the following advantages that by miniature double
Screw mixes obtain the thermoplasticity co-blend polypropylene cable insulating material of the crystalline substance containing β haveing excellent performance.The preparation of masterbatch ensure that nucleation
The uniform and stable dispersion of agent and rise its generation of β crystal is induced in polypropylene.Meanwhile the introducing of β crystal and two kinds are poly-
The blending of polypropylene matrix, which ensure that, has both electric property (15% or more dc breakdown intensity ratio EPC raising, pressurization 50kv/mm
Apparent space charge is not observed after 300min) and mechanical performance (fault growth rate improves 30% or more than pure iPP, often
Warm impact strength ratio iPP improves 10 times or more, and brittle temperature point reaches -30 DEG C or less).
Claims (10)
1. a kind of polypropylene-base high voltage direct current cable material, which is characterized in that according to the mass fraction, the isotactic poly- third containing beta nucleater
10~50 parts of alkene, 50~90 parts of ethylene-propylene block copolymer polypropylene and 0.1~0.5 part of antioxidant；Wherein, contain beta nucleater
Isotactic polypropylene and the sum of the mass fraction of ethylene-propylene block copolymer polypropylene be 100 parts, the isotactic poly- third containing beta nucleater
The mass fraction of beta nucleater is 0.3%~1% in alkene.
2. a kind of polypropylene-base high voltage direct current cable material according to claim 1, which is characterized in that containing beta nucleater etc.
Isotactic polypropylene is made by following procedure:
1) prepare the polypropylene masterbatch containing beta nucleater: it is total that melting in twin screw compounder is added in isotactic polypropylene, beta nucleater
It is mixed, it is squeezed out after mixing by twin-screw, obtains the polypropylene masterbatch containing beta nucleater；Wherein, the quality of beta nucleater is containing β
The 5%~10% of the polypropylene masterbatch quality of nucleating agent；
2) it prepares semi-finished product material: melt blending in twin screw compounder is added with polypropylene in the polypropylene masterbatch containing beta nucleater,
It is squeezed out after mixing through twin-screw, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater account for containing beta nucleater etc.
The mass percent of isotactic polypropylene is 0.3%~1%.
3. a kind of polypropylene-base high voltage direct current cable material according to claim 2, which is characterized in that isotactic polypropylene melts
Melting index is 2.9 ± 0.2g/10min.
4. a kind of polypropylene-base high voltage direct current cable material according to claim 2, which is characterized in that beta nucleater 2,6-
Cyclohexanedimethanol amide, N, N '-dicyclohexyl -2,6- naphthalene diamides, TMB-4, TMB-5, in rare earth nucleating agent WBG-II
It is one or two kinds of.
5. a kind of polypropylene-base high voltage direct current cable material according to claim 1, which is characterized in that ethylene-propylene block is total
The mass fraction of ethylene segment is 10%~20% in poly- polypropylene, and the melt index of ethylene-propylene block copolymer polypropylene is
2.1±0.2g/10min。
6. a kind of polypropylene-base high voltage direct current cable material according to claim 1, which is characterized in that antioxidant is four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2.4- di-tert-butyl-phenyl) phosphite esters, 4,4'- sulphur
One or more of Dai Shuan (6- tert-butyl -3- methylphenol).
7. a kind of polypropylene-base high voltage direct current cable material according to claim 6, which is characterized in that when antioxidant is four
[β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2.4- di-tert-butyl-phenyl) phosphite esters, 4,
When two or three in 4'- thiobis (6- tert-butyl -3- methylphenol), every kind of antioxidant accounts for the quality of antioxidant gross mass
Score is no less than 10%.
8. a kind of preparation method of the polypropylene-base high voltage direct current cable material as described in any one of claim 1-7, special
Sign is, comprising the following steps:
1) prepare the polypropylene masterbatch containing beta nucleater: it is total that melting in twin screw compounder is added in isotactic polypropylene, beta nucleater
It is mixed, it is squeezed out after mixing by twin-screw, obtains the polypropylene masterbatch containing beta nucleater；Wherein, the quality of beta nucleater is containing β
The 5%~10% of the polypropylene masterbatch quality of nucleating agent；
2) it prepares semi-finished product material: melt blending in twin screw compounder is added with polypropylene in the polypropylene masterbatch containing beta nucleater,
It is squeezed out after mixing through twin-screw, obtains the isotactic polypropylene containing beta nucleater；Wherein, beta nucleater account for containing beta nucleater etc.
The mass percent of isotactic polypropylene is 0.3%~1%；
3) prepare finished product material: isotactic polypropylene, ethylene-propylene block copolymer polypropylene, antioxidant containing beta nucleater are double by being added
In screw rod batch mixer, uniformly squeezes out and be sent into pelleter after cooling after pelletizing, obtain polypropylene-base high voltage direct current cable material.
9. a kind of preparation method of polypropylene-base high voltage direct current cable material according to claim 8, which is characterized in that step
1) in, the temperature in each area of screw rod is set as 195~200 DEG C, and feed opening revolving speed is 8~12rpm, and screw speed is 150~
200rpm；
In step 2), the temperature in each area of screw rod is set as 195~200 DEG C, and feed opening revolving speed is 12~16rpm, and screw speed is
200~300rpm.
10. a kind of preparation method of polypropylene-base high voltage direct current cable material according to claim 8, which is characterized in that step
It is rapid 3) in, the temperature in each area of screw rod is set as 195~200 DEG C, and feed opening revolving speed is 12~16rpm, screw speed is 200~
300rpm。
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| CN111423658A (en) * | 2020-04-10 | 2020-07-17 | 天津大学 | Polypropylene cable material under polarity reversal working condition, and preparation method and application thereof |
| CN111560136A (en) * | 2020-04-09 | 2020-08-21 | 天津大学 | Polypropylene-based high-voltage direct-current cable material and modification and crystallization temperature regulation and control method |
| CN113248832A (en) * | 2021-02-03 | 2021-08-13 | 中国电力科学研究院有限公司 | High-voltage direct-current polypropylene cable material |
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