CN110452468A - A kind of thermoplastic cable Insulation Material and preparation method thereof - Google Patents
A kind of thermoplastic cable Insulation Material and preparation method thereof Download PDFInfo
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- CN110452468A CN110452468A CN201910910850.8A CN201910910850A CN110452468A CN 110452468 A CN110452468 A CN 110452468A CN 201910910850 A CN201910910850 A CN 201910910850A CN 110452468 A CN110452468 A CN 110452468A
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- styrene
- butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Abstract
The present invention provides a kind of thermoplastic cable Insulation Materials and preparation method thereof.Thermoplastic cable Insulation Material provided by the invention is by including that the raw material of following content of component is made: 100 parts of acrylic resin；10~50 parts of hydrogenated styrene-butadiene-styrene block copolymers；0.2~0.6 part of antioxidant.The present invention uses specific hydrogenated styrene-butadiene-styrene block copolymers (i.e. SEBS) and antioxidant with the common modified polypropylene resin of certain proportion, it can be effectively reduced the hardness and modulus and thermal deformation of material, and improve the heat resistance and thermal stability of material, it is set to meet the service performance demand of crosslinked polyethylene cable insulating material, simultaneously, the material has solvable fusible thermoplasticity, can reprocessabilty recycling use, it is environmental-friendly, overcome the difficult problem of crosslinked polyethylene electrical isolation material recovery processing.
Description
Technical field
The present invention relates to cable material technical field, in particular to a kind of thermoplastic cable Insulation Material and preparation method thereof.
Background technique
It is well known that twisted polyethylene cable has extensively in mesohigh, super-pressure even extra-high-voltage alternating current power transmission
Using its advantage is that electrical property is excellent, high temperature resistant (can be up to 90 DEG C of long-term use temperatures), good, soft, the resistance to stability of processability are good
Deng.However, crosslinked polyethylene belongs to thermoset macromolecule material, have it is insoluble do not melt characteristic, thus, thousands of tons use the longevity
The recycling and reuse for ordering overdue discarded twisted polyethylene cable become intractable world-famous puzzle, cause serious dirt to environment
Dye；Meanwhile some faulty goods in twisted polyethylene cable production process lead to waste and ring because CABLE MATERIALS not can be recycled
Border pollution.
Therefore, in order to cope with it is insoluble existing for cross-linked poly-ethylene cable material do not melt, difficult the problem of recycling, handed over meeting
On the basis of the electrical property and the physical mechanical property that join poly-ethylene cable material, developing solvable fusible replacement cables material must go.Its
In, the solvable fusible high molecular material of thermoplasticity becomes first choice, and still, thermoplastic macromolecule material usually has harder, modulus
High physical mechanical property problem and lead to Cable Bending Radius is big, thermal stability is poor etc., influence electric cable transporting, install and make
With.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of thermoplastic cable Insulation Materials and preparation method thereof.The present invention
The thermoplasticity electrical isolation material of offer is not only solvable, and the Physical Mechanicals such as modulus, thermal stability and electrical property are able to satisfy electricity
The requirement of cable material, preferably can replace crosslinked polyethylene to use as CABLE MATERIALS.
The present invention provides a kind of thermoplastic cable Insulation Materials, are made by the raw material for including following content of component:
100 parts of acrylic resin；
10~50 parts of hydrogenated styrene-butadiene-styrene block copolymers；
0.2~0.6 part of antioxidant.
Preferably, the acrylic resin is copolymerized type propene polymer resin；
The ethylene contents of the copolymerized type propene polymer resin are 1%~7%.
Preferably, the melt index of the acrylic resin is 2~3g/10min.
Preferably, the number-average molecular weight of the hydrogenated styrene-butadiene-styrene block copolymers >=220,000.
Preferably, in the hydrogenated styrene-butadiene-styrene block copolymers styrene-content be 20%~
40%.
Preferably, the antioxidant be four { β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol esters and/or
4,4 '-thiobis (6- tert-butyl -3- methylphenol).
Preferably, the content of the hydrogenated styrene-butadiene-styrene block copolymers is 25~35 parts.
The present invention also provides a kind of preparation method of thermoplastic cable Insulation Material as described in the above technical scheme, packets
It includes:
By acrylic resin, hydrogenated styrene-butadiene-styrene block copolymers and antioxidant mixing mixing, obtain
Cable insulating material.
Preferably, the temperature of the mixing is 200~250 DEG C, and the time is 10~15min.
Preferably, the revolving speed of the mixing is 40~70r/min.
The present invention provides a kind of thermoplastic cable Insulation Materials, are made by the raw material for including following content of component: poly- third
100 parts of olefine resin；10~50 parts of hydrogenated styrene-butadiene-styrene block copolymers；0.2~0.6 part of antioxidant.This hair
It is bright to use specific hydrogenated styrene-butadiene-styrene block copolymers (i.e. SEBS) and antioxidant common with certain proportion
Modified polypropylene resin, can be effectively reduced the hardness and modulus and thermal deformation of material, and improve material heat resistance and heat it is steady
It is qualitative, so that it is met the service performance demand of crosslinked polyethylene cable insulating material, meanwhile, which has solvable fusible thermoplastic
Property, can reprocessabilty recycling use, it is environmental-friendly, overcome the difficult problem of crosslinked polyethylene electrical isolation material recovery processing.
Specific embodiment
The present invention provides a kind of thermoplastic cable Insulation Materials, are made by the raw material for including following content of component:
100 parts of acrylic resin；
10~50 parts of hydrogenated styrene-butadiene-styrene block copolymers；
0.2~0.6 part of antioxidant.
The present invention use specific hydrogenated styrene-butadiene-styrene block copolymers (i.e. SEBS) and antioxidant with
The common modified polypropylene resin of certain proportion, can be effectively reduced the hardness and modulus of material, and improve material heat resistance and
Thermal stability makes it meet the service performance demand of crosslinked polyethylene cable insulating material, meanwhile, which has solvable fusible heat
Plasticity, can reprocessabilty recycling use, it is environmental-friendly, overcome the difficult problem of crosslinked polyethylene electrical isolation material recovery processing.
In the present invention, the acrylic resin is preferably copolymerized type propene polymer resin, more preferably random copolymerization type poly- third
Olefine resin PP-R.Copolymerized type propene polymer is to be copolymerized to obtain in the case where heating pressurized conditions by propylene monomer and a small amount of vinyl monomer, In
Vinyl monomer is distributed in propylene long-chain.In random copolymerization type acrylic resin, vinyl monomer is random, is randomly distributed to propylene
In long-chain.
In the present invention, the ethylene contents of the copolymerized type propene polymer resin are preferably 1%~7%, more preferably 4%~
7%.In some embodiments of the invention, the ethylene contents of the copolymerized type propene polymer resin are 1%, 4%, 7% or 10%.
In the present invention, the melt index of the acrylic resin is preferably 2~3g/10min.Melt index refers to plastic cement material
Mobility numerical value when material processing, also referred to as melt flow rate (MFR), unit g/10min can draw resin according to melt index
It is divided into different type or the trade mark.The present invention is not particularly limited the source of the acrylic resin, be general commercially available product or
It is made according to the preparation method of those skilled in the art's resin.
In the present invention, the styrene-content of the hydrogenated styrene-butadiene-styrene block copolymers (i.e. SEBS) is excellent
It is selected as 20%~40%, more preferably 20%~30%.In some embodiments of the invention, hydrogenated styrene-butadiene-benzene
The styrene-content of ethylene block copolymer is 20% or 30%.
In the present invention, the number-average molecular weight of the hydrogenated styrene-butadiene-styrene block copolymers is preferably >=22
Ten thousand, more preferably 23~280,000.The present invention does not have the source of the hydrogenated styrene-butadiene-styrene block copolymers
It is specifically limited, it is general commercially available product.
In the present invention, on the basis of 100 parts of acrylic resin content, the hydrogenated styrene-butadiene-styrene block
The content of copolymer is 10~50 parts, is arranged in pairs or groups with the ratio, can be effectively reduced the hardness and modulus of acrylic resin, change
It is apt to its thermal stability.The content of the hydrogenated styrene-butadiene-styrene block copolymers is more preferably 25~35 parts, In
Under the dosage, the physical mechanical property and electrical insulation capability of material can be further promoted.In some embodiments of the invention,
The dosage of the hydrogenated styrene-butadiene-styrene block copolymers is 10 parts, 15 parts, 25 parts or 35 parts.
In the present invention, the antioxidant is preferably four { β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythrites
Ester (i.e. antioxidant 1010) and/or 4,4 '-thiobis (6- tert-butyl -3- methylphenol) (i.e. antioxidant 300), using above-mentioned anti-
Oxygen agent can act synergistically with SEBS, play modifying function to acrylic resin, reduce the hardness and modulus of material, improve material
Heat resistance it is beneficial, and the introducing of antioxidant can effectively prevent degradation of polypropylene, protect polypropylene macromolecular chain, further mention
Its high thermal stability.The present invention is not particularly limited the source of the antioxidant, is general commercially available product.
In the present invention, on the basis of 100 parts of acrylic resin content, the dosage of the antioxidant is 0.2~0.6 part.In
In some embodiments of the present invention, the dosage of the antioxidant is 0.5 part.
It is embedding using specific hydrogenated styrene-butadiene-styrene the present invention provides a kind of thermoplastic cable Insulation Material
Section copolymer (i.e. SEBS) and antioxidant with the common modified polypropylene resin of special ratios, can be effectively reduced material hardness and
Modulus, and the heat resistance and thermal stability of material are improved, so that it is met the service performance demand of crosslinked polyethylene cable insulating material,
Meanwhile the material have solvable fusible thermoplasticity, can reprocessabilty recycling use, it is environmental-friendly, overcome crosslinked polyethylene electricity
The difficult problem of Insulation Material recovery processing.
The present invention also provides a kind of preparation methods of thermoplastic cable Insulation Material described in above-mentioned technical proposal, comprising:
By acrylic resin, hydrogenated styrene-butadiene-styrene block copolymers and antioxidant mixing mixing, cable insulation is obtained
Material.
Wherein, the type of the acrylic resin, hydrogenated styrene-butadiene-styrene block copolymers and antioxidant,
The features such as dosage and source with it is consistent described in above-mentioned technical proposal, this is no longer going to repeat them.
In the present invention, the mixing can be carried out by means of mixer, mix mixing in the mixer of torque rheometer.Institute
The temperature for stating mixing is preferably 200~250 DEG C, and more preferably 210~230 DEG C.The time of the mixing is preferably 10~
15min.In the present invention, the revolving speed of the mixing is preferably 40~70r/min, more preferably 60r/min.It is by above-mentioned mixing
Obtain cable insulating material, the subsequent product that cable insulating material can be processed into required shape and size more according to actual needs.This hair
Preparation method is simple for bright offer, mild condition, is convenient for large-scale production application.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
Raw material: 100 parts of copolymerization PP, melt index 2.2g/10min, ethylene contents 4%；10 parts of SEBS, molecular weight are
250000, styrene-content 30%；0.5 part of antioxidant 1010；
Above-mentioned raw materials are put into mixer, cable is made through melt blending in the mixing 12min at 210 DEG C, revolving speed 60rpm
Insulation Material.
Embodiment 2
Raw material: 100 parts of copolymerization PP, melt index 2.2g/10min, ethylene contents 4%；15 parts of SEBS, molecular weight are
250000, styrene-content 30%；0.5 part of antioxidant 1010；
Above-mentioned raw materials are put into mixer, cable is made through melt blending in the mixing 12min at 210 DEG C, revolving speed 60rpm
Insulation Material.
Embodiment 3
Raw material: 100 parts of copolymerization PP, melt index 2.2g/10min, ethylene contents 4%；25 parts of SEBS, molecular weight are
250000, styrene-content 30%；0.5 part of antioxidant 1010；
Above-mentioned raw materials are put into mixer, cable is made through melt blending in the mixing 12min at 210 DEG C, revolving speed 60rpm
Insulation Material.
Embodiment 4
Raw material: 100 parts of copolymerization PP, melt index 2.2g/10min, ethylene contents 4%；35 parts of SEBS, molecular weight are
250000, styrene-content 30%；0.5 part of antioxidant 1010；
Above-mentioned raw materials are put into mixer, cable is made through melt blending in the mixing 12min at 210 DEG C, revolving speed 60rpm
Insulation Material.
Embodiment 5
Raw material: 100 parts of copolymerization PP, melt index 2.2g/10min, ethylene contents 4%；25 parts of SEBS, molecular weight are
250000, styrene-content 20%；0.5 part of antioxidant 1010；
Above-mentioned raw materials are put into mixer, cable is made through melt blending in the mixing 12min at 210 DEG C, revolving speed 60rpm
Insulation Material.
Comparative example 1
Sample is prepared according to the raw material and preparation process of embodiment 1, unlike, in raw material, SEBS dosage is 3 parts, is resisted
Oxygen agent dosage is 0.1 part.
Embodiment 6
Cable insulating material made from Examples 1 to 5 and comparative example 1 is placed in mold respectively, passes through vulcanizing press pressure
Rich sheet test sample is made；The temperature of vulcanizing press be 190~200 DEG C, pressure be 8~12MPa, the pressing time be 5~
15min。
The modulus of test gained test sample, heat extension, hardness and volume resistivity respectively.It is specific as follows:
Modulus evaluation method uses dynamic mechanical analysis (Dynamic Mcchanical Analysis, abbreviation DMA), surveys
Modulus (rigidity) characteristic of test material material under a cyclic stress, when deformation.Firstly, sample is pressed into the sheet material of 1mm thickness, then
Cut growth 4cm × wide 1cm batten；Using stretch mode, frequency 1Hz, heating rate is 3 DEG C/min, and amplitude is 6 μm,
Scanning temperature is 25~165 DEG C.
The test reference standard GB/T 2951.21-2008 of heat extensibility energy.
The test of hardness is measured with Shore durometer (D type) and is obtained according to GB/T2411-2008/ISO 868:2003.
The test of volume resistivity is referring to GB/T 12706.2-2002.
Test result is referring to table 1:
The performance test results of 1 Examples 1 to 5 of table and comparative example 1
By the above test result it is found that compared with acrylic resin, the storage modulus decline of present invention gained modified material,
Rigidity reduces, and 165 DEG C of elongation and permanent deformation is all very low, and resistivity is lower, insulation performance is preferable, and shore D decline meets
The JB/T 10738-2007 standard of cross-linked poly-ethylene cable material.In addition, the raw material that above-mentioned material uses is solvable fusible thermoplasticity
Macromolecule is not crosslinked in preparation process, and CABLE MATERIALS is recyclable, is environment-friendly materials.
Compared with comparative example 1, storage modulus, elongation and permanent deformation, the hardness of modified material obtained by Examples 1 to 5
And volume resistivity is substantially reduced, it was demonstrated that, consumption proportion collocation according to the invention could improve the modulus, hardness, change of material
The physical mechanical properties such as shape and electrical isolation.
In Examples 1 to 5, modulus, hardness, volume resistivity of embodiment 3~5 etc. are further decreased, it was demonstrated that, SEBS is used
When amount is 25~35 parts, the physical mechanical property of material can be further promoted.Wherein, the physical mechanical property of embodiment 3 is most
It is good, it was demonstrated that, SEBS dosage is 35 parts, and effect is best.
Embodiment 7~9
Sample is prepared according to the raw material and preparation process of embodiment 3, unlike, in raw material, the ethylene of acrylic resin
Content is 1%, 7%, 10%；It is denoted as embodiment 7~9 respectively.
According to the performance of the test method test resulting materials of embodiment 6, as a result referring to table 2:
The performance test results of 2 embodiment 7~9 of table
It can be seen from 2 test result of table compared to embodiment 9, embodiment 3,7~8 gained modified material of embodiment
Storage modulus, elongation and permanent deformation, hardness are substantially reduced, it was demonstrated that, it, can when ethylene contents are 1%~7% in polypropylene
Preferably improve the physical mechanical properties such as modulus, hardness, the deformation of material.Wherein, the physical mechanical of embodiment 3 and embodiment 8
Performance is more preferably, it was demonstrated that, when ethylene contents are 4%~7% in polypropylene, effect is more preferable.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field is appointed
What technical staff can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementations
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, are wanted then these other embodiments should also be included in right
In the range of asking.
Claims (10)
1. a kind of thermoplastic cable Insulation Material, which is characterized in that be made by the raw material for including following content of component:
100 parts of acrylic resin；
10~50 parts of hydrogenated styrene-butadiene-styrene block copolymers；
0.2~0.6 part of antioxidant.
2. cable insulating material according to claim 1, which is characterized in that the acrylic resin is copolymerized type propene polymer tree
Rouge；
The ethylene contents of the copolymerized type propene polymer resin are 1%~7%.
3. cable insulating material according to claim 1 or 2, which is characterized in that the melt index of the acrylic resin is 2
~3g/10min.
4. cable insulating material according to claim 1, which is characterized in that the hydrogenated styrene-butadiene-styrene is embedding
Number-average molecular weight >=220,000 of section copolymer.
5. cable insulating material according to claim 1 or 4, which is characterized in that the hydrogenated styrene-butadiene-benzene second
Styrene-content is 20%~40% in alkene block copolymer.
6. cable insulating material according to claim 1, which is characterized in that the antioxidant is four { β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) propionic acid } pentaerythritol ester and/or 4,4 '-thiobis (6- tert-butyl -3- methylphenol).
7. cable insulating material according to claim 1, which is characterized in that the hydrogenated styrene-butadiene-styrene is embedding
The content of section copolymer is 25~35 parts.
8. a kind of preparation method of thermoplastic cable Insulation Material according to any one of claims 1 to 7, which is characterized in that packet
It includes:
By acrylic resin, hydrogenated styrene-butadiene-styrene block copolymers and antioxidant mixing mixing, cable is obtained
Insulation Material.
9. preparation method according to claim 8, which is characterized in that the temperature of the mixing is 200~250 DEG C, the time
For 10~15min.
10. preparation method according to claim 8, which is characterized in that the revolving speed of the mixing is 40~70r/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113105694A (en) * | 2021-03-02 | 2021-07-13 | 中国电力科学研究院有限公司 | Medium-voltage polypropylene cable and preparation method thereof |
| 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 |
| CN113845734A (en) * | 2021-10-22 | 2021-12-28 | 万华化学（宁波）有限公司 | Thermoplastic polypropylene cable insulating material for high voltage and preparation method thereof |
| CN113999457A (en) * | 2021-12-01 | 2022-02-01 | 国网黑龙江省电力有限公司电力科学研究院 | Polypropylene-based insulating material for environment-friendly cable and preparation method thereof |
| CN114292466A (en) * | 2021-12-07 | 2022-04-08 | 中广核高新核材科技（苏州）有限公司 | Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof |
| CN115044137A (en) * | 2021-03-09 | 2022-09-13 | 中国石油化工股份有限公司 | Composition for preparing polypropylene material and application thereof, polypropylene material and preparation method and application thereof |
| CN116041861A (en) * | 2022-12-15 | 2023-05-02 | 南方电网科学研究院有限责任公司 | Polypropylene-based insulating material and preparation method and application thereof |
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| 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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| CN115044137B (en) * | 2021-03-09 | 2024-04-12 | 中国石油化工股份有限公司 | Composition for preparing polypropylene material, application thereof, polypropylene material and preparation method and application thereof |
| CN113845734A (en) * | 2021-10-22 | 2021-12-28 | 万华化学（宁波）有限公司 | Thermoplastic polypropylene cable insulating material for high voltage 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 |
| CN113999457A (en) * | 2021-12-01 | 2022-02-01 | 国网黑龙江省电力有限公司电力科学研究院 | Polypropylene-based insulating material for environment-friendly cable and preparation method thereof |
| CN114292466A (en) * | 2021-12-07 | 2022-04-08 | 中广核高新核材科技（苏州）有限公司 | Modified polypropylene insulating material for medium and low voltage power cable and preparation method thereof |
| CN116041861A (en) * | 2022-12-15 | 2023-05-02 | 南方电网科学研究院有限责任公司 | Polypropylene-based insulating material and preparation method and application thereof |
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