CN106883618A - Application of the extra large work with sea water resistance high intensity high resistance thermoplastic elastomer composite material and preparation method thereof and in waterproof flexible cable - Google Patents
Application of the extra large work with sea water resistance high intensity high resistance thermoplastic elastomer composite material and preparation method thereof and in waterproof flexible cable Download PDFInfo
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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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
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
- H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
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- 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
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- 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
- H01B3/448—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 other vinyl compounds
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Abstract
The invention discloses a kind of preparation of sea water resistance high intensity high resistance thermoplastic elastomer composite material of extra large work, and by the use of the material as sheath material, it is prepared for a kind of waterproof flexible cable.The invention belongs to technical field of new material preparation, by high-insulativity, corrosion resistance, barrier and the lubricity of peeling off hexagonal boron nitride nanosheet, insulation high, inexpensive ultrafine mica powder is coordinated to be modified thermoplastic elastomer (TPE), improve its resistance to corrosion seawater and wearability, improve its insulaion resistance under long-time sea water immersion environment.Waterproof flexible cable prepared by extra large work sea water resistance high intensity high resistance heat thermoplastic elastic composite processing has the performances such as good flexible resistance, water absorption resistance, splendid mechanical performance, the aging, seawater corrosion resistance of sea water resistance.
Description
Technical field
The present invention relates to the material modified field of thermoplastic elastomehc solid-state gonosome, more particularly to extra large work is high with sea water resistance high intensity
Resistance thermoplastic elastomer (TPE) cable jacket material and preparation method thereof.
Technical background
After being attacked by moisture, its electrical property and mechanical performance rapid drawdown, particularly naval vessel or can all be assembled cable under water
Use cable.Such as ship cable, is frequently used for drying and moist alternate environment or long term submersion in water, or even immersion hot water or steaming
In vapour, its electrical property, mechanical performance can accelerate to decline, and in use, leakage current is bigger than normal, electrical equipment starting difficulty, seriously
When electric shock can be caused to hurt sb.'s feelings.
Currently used water-fast cable has two kinds of longitudinal water-blocking and radial water-resisting：Longitudinal water-blocking generally with water blocking yarn, block water
Powder or waterstop, these materials contain water, prevent moisture along the further diffusion of cable longitudinal direction；Radial water-resisting is main
Realized by hot pressing, welding, cold-drawn protective metal shell, as submarine cable commonly uses lead set, but such cable poor in flexibility,
Be not suitable for frequent movement.In addition, there is substantial amounts of seawater in the use environment of seabed or ship cable, seawater is in itself have very
The electrolyte solution of severe corrosive, containing a large amount of salts, has very strong wellability to traditional PVC classes polar material sheath, long
Time is easily penetrated into inside cable after, is caused insulaion resistance to decline, is even corroded interior metal conductor wire core.
Thermoplastic elastomer is a kind of new material, and it is just gradually applied in electric wire industry.First, thermoplastic
Elastomer is more superior than hard rubber economy in terms of processing.The energy ezpenditure of thermoplastic elastomer is processed than processing hard rubber
Much less.Due to facing the problems such as natural gas shortage, oil embargo, thus energy supply seems nervous, and then many producers are all
Thermoplastic elastomer is regarded as reduces a kind of means of energy resource consumption.Compared with continuous vulcanization rubber, thermoplastic elastomer is more superior
Be with short production cycle, color distortion various;Again in terms of waste material can be reprocessed, thermoplastic elastic physical efficiency plays machine dress
Standby bigger utilization rate.But, thermoplastic elastomer (TPE) is also a kind of macromolecular material, right especially for noncrystalline rubber phase
The obstructing capacity of hydrone is poor, and after being soaked in seawater for a long time, hydrone gradually can be spread inside macromolecule matrix, so as to cause
The problems such as macromolecular material decreasing insulating.Chinese invention patent CN 104829919 discloses a kind of submarine cable PE
Protective cover material and preparation method thereof, the seawater corrosion resistance of PE and resistance to micro- life are improved using fillers such as modified hemps and magnesia
Thing corrodes.But PE is as cable jacket material be not as soft as thermoplastic elastomer (TPE).Chinese invention patent CNI05061881 is disclosed
A kind of wisdom energy seawater corrosion resistant cable sheath rubber and preparation method thereof, it is modified using high-quality thin graphene microplate
Second fourth elastomer, improves its resistance to corrosion seawater, but graphene microchip is high conductive material, the insulating properties influence on elastomer
It is very big.Chinese invention patent CNI04059321 discloses a kind of weather resistance environmental protection flame retardant flexible cable polymeric material and its system
Preparation Method, other halogen-free flame retardants are coordinated using the fire retardant containing halogen, improve the fire resistance of flexible cable, but its is resistance to
Seawater and insulating properties still have much room for improvement.
The content of the invention
The present invention is directed to problem mentioned above, there is provided a kind of extra large work sea water resistance high intensity high resistance heat thermoplastic elastic
Composite, the material can be used for the sheath of cable.
In order to solve the above problems, the technical scheme is that：
A kind of extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material, its weight portion constitutes and is：Polystyrene
70 ~ 110 parts of 100 parts of analog thermoplastic elastomer SEBS, polypropylene PP, 100 ~ 120 parts of operation oil, 5 ~ 15 parts of ultrafine mica powder,
Hexagonal boron nitride nanosheet（BNNS）1 ~ 5 part, 0.5 ~ 0.7 part of antioxidant, 0.05 ~ 0.15 part of titante coupling agent, silane idol
0.05 ~ 0.25 part of agent of connection.
The ultrafine mica powder is one or more in phlogopite, muscovite and sericite, and particle size range is 300 ~ 800
Nanometer.
The stripping hexagonal boron nitride nanosheet, particle size range is 100 ~ 300 nanometers, 8 ~ 15 nanometers of thickness.
The extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material, it is multiple using BNNS and ultrafine mica powder
With filled modified thermoplastic elastomer, using the insulation corrosion-resistant, high of BNNS, barrier and lubricity, coordinate insulation high, it is low into
This ultrafine mica powder, under relatively low hexagonal boron nitride loading（1 ~ 5 part）, the seawater corrosion resistance of improvement thermoplastic elastomer (TPE),
Insulaion resistance under wearability and long-time sea water immersion environment.
Its preparation process is as follows：
（1）BNNS is added in operation oil, is then mixed as dispersant by 4% ~ 7% addition silane coupler of BNNS weight
Ultrasonic disperser ultrasonic disperse is used after conjunction 8 ~ 12 minutes.
（2）The scattered operation oil containing BNNS, the half of antioxidant ratio and SEBS are proportionally added at a high speed
Mix oil-filled in mixer, mixing 8 ~ 10 minutes after, place 24 ~ 36 hours, by SEBS fully it is swelling while, make BNNS uniform
SEBS powders surface is dispersed in, then with banbury banburying 10 ~ 15 minutes, last extruding pelletization is standby.
（3）The half of PP, ultrafine mica powder, titanate coupling agent, antioxidant ratio is proportionally added into mixed at high speed
In machine, mix 8 ~ 12 minutes, with banbury banburying 10 ~ 15 minutes after taking-up, last extruding pelletization is standby.
（4）Will be above-mentioned（2）With（3）Standby material carries out melt blending in being added to double screw extruder, and then granulation is obtained
Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet.
The present invention utilizes the nano-material modified SEBS/PP co-blending elastic bodies of two-dimensional layer, improves SEBS/PP co-blending elastic bodies
Resistance to corrosion seawater, wearability and electrical insulation capability, so as to widen TPE material in terms of marine field cable cover(ing) should
With, the current Plastic protective cover material of solution is really up to the mark, multiple folding and unfolding cracking, and rubber-like sheath power consumption of polymer processing is big, efficiency is low, species is few etc.
Industry bottleneck problem is specifically as follows：
1）Macromolecular material（The particularly amorphous area of amorphism macromolecule and crystalline polymer）The presence of free volume is led
Cause to be immersed in rear easily water suction in water for a long time, inner conductor is even corroded so as to cause jacket insulation to decline.This project is adopted
Filling SEBS with BNNS can utilize the excellent barriers of BNNS, corrosion resistance and mechanics enhancing characteristic, improve the resistance to sea of SEBS phases
Aqueous energy and mechanical strength.
2）TPE in general wearability be not so good as vulcanized rubber, for roving cable, sheath it is resistance to
Mill property is also most important.This project fills TPE using two-dimension nano materials such as mica, montmorillonites with high insulating property, no
TPE sheaths insulating properties after absorbing water can be only improved, the wearability of sheath can also be improved, such that it is able to further raising
The life and reliability of cable.
3）BNNS/SEBS nano composite materials and its process for dispersing：Generally need to fill industrial white before SEBS and PP blendings
The operation oil such as oil improves the processability of SEBS, and first BNNS is dispersed in operation oil using the Oil feeding process of SEBS, then carries out
Oil-extended process, can not only make BNNS scattered more uniform in SEBS, and BNNS can be made farthest to be filled in
SEBS phases, improvement SEBS phases are poor relative to PP phase sea water resistances, low intensity problem, such that it is able to be added using less BNNS
Amount, improves the sea water resistance and mechanical strength of SEBS/PP co-blending elastic bodies.
4）Nano powder modified SEBS/PP thermoplastic elastics preparation：Changed using Nano fillings such as carbon black, white carbons
Property SEBS/PP thermoplastic elastomer (TPE)s be typically by nano-powder, oil-filled SEBS and PP material enter while being added to double screw extruder
Row mixing, nano-powder is indifference dispersity in SEBS phases and PP phases.This patent first by different Nano fillings respectively with
SEBS and PP carries out banburying respectively and is blended in advance, is then again granulated both materials for getting togather of premix, twin-screw extrusion two
Secondary blending.The technique can not only realize the difference dispersion in different phases of different Nano fillings, and to twin screw device
It is required that reducing, powder disperses evenly in the base.Furthermore it is possible to by the addition of nano-powder in banburying technology for premixing
Measure to adjust the differences in viscosity of two-phase, make two-phase melt viscosity in the blending of secondary screw rod closer, it is easier to form interpenetrating networks
Structure, improves the mechanical performance of nano composite material.
Specific embodiment
Describe the present invention in detail below in conjunction with specific embodiment, herein illustrative examples of the invention and explanation
It is for explaining the present invention but not as a limitation of the invention.
Specific implementation example 1：
70 parts, technical white oil 46#120 parts, 300 nanometers of 100 parts of polystyrene-type thermoplastic elastomers SEBS, polypropylene PP
5 parts of phlogopite powder, hexagonal boron nitride nanosheet（BNNS）5 parts, 0.5 part of antioxidant 1010, the different tristearin of titante coupling agent three
Sour isopropyl titanate TTS0.05 parts, 0.25 part of Silane coupling agent KH550.Specific preparation process is as follows：
（1）BNNS is added in operation oil, Silane coupling agent KH550 is subsequently adding as dispersant, ultrasonic wave is used after mixing
Disperser ultrasonic disperse 12 minutes.
（2）The scattered oil of the operation containing BNNS, 0.25 part of antioxidant 1010 and SEBS are added to high-speed mixer
Middle mixing is oil-filled, mixes 10 minutes, is taken out after placing 36 hours, banbury banburying 15 minutes, and then extruding pelletization is standby.
（3）PP, 300 nm of gold mica powders, TTS, 0.25 part of antioxidant 1010 are proportionally added into high-speed mixer,
Mixing 10 minutes, with banbury banburying 15 minutes after taking-up, last extruding pelletization is standby.
（4）Will be above-mentioned（2）、（3）Standby material carries out melt blending in being added to double screw extruder, and then granulation obtains sea
Work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet.
（5）Will be above-mentioned（4）Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet as cable
Insulation and restrictive coating, manufacture waterproof flexible cable.
Specific implementation example 2：
90 parts, technical white oil 32#120 parts, 500 nanometers of 100 parts of polystyrene-type thermoplastic elastomers SEBS, polypropylene PP
10 parts of sericite in powder, hexagonal boron nitride nanosheet（BNNS）3 parts, 0.6 part of irgasfos 168, titante coupling agent KR-138s
0.1 part, 0.15 part of Silane coupling agent KH550.Specific preparation process is as follows：
（1）BNNS is added in operation oil, Silane coupling agent KH550 is subsequently adding as dispersant, ultrasonic wave is used after mixing
Disperser ultrasonic disperse 10 minutes.
（2）The scattered oil of the operation containing BNNS, 0.3 part of irgasfos 168, antioxidant and SEBS are added to and mixed at a high speed
Mix oil-filled in conjunction machine, mix 9 minutes, place 30 hours, banbury banburying 12 minutes after taking-up, then extruding pelletization is standby.
（3）PP, 500 nanometers of sericites in powder, KR-138s, 0.3 part of irgasfos 168 are proportionally added into high-speed mixer
In, mixing 8 minutes, with banbury banburying 12 minutes after taking-up, last extruding pelletization is standby.
（4）Will be above-mentioned（2）With（3）Standby material carries out melt blending in being added to double screw extruder, and then granulation is obtained
Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet.
（5）Will be above-mentioned（4）Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet as cable
Insulation and restrictive coating, manufacture waterproof flexible cable.
Specific implementation example 3：
110 parts, technical white oil 46#120 parts, 800 nanometers of 100 parts of polystyrene-type thermoplastic elastomers SEBS, polypropylene PP
15 parts of white mica powder, hexagonal boron nitride nanosheet（BNNS）1 part, 0.7 part of antioxidant 1010, titante coupling agent TTS0.15
Part, 0.05 part of Silane coupling agent KH550.Specific preparation process is as follows：
（1）BNNS is added in operation oil, Silane coupling agent KH550 is subsequently adding as dispersant, ultrasonic wave is used after mixing
Disperser ultrasonic disperse 8 minutes.
（2）The scattered oil of the operation containing BNNS, 0.35 part of antioxidant 1010 and SEBS are added to high-speed mixer
Middle mixing is oil-filled, after mixing 8 minutes, places 24 hours, banbury banburying 10 minutes after taking-up, and then extruding pelletization is standby.
（3）PP, 800 nanometers of white mica powders, TTS, 0.35 part of antioxidant 1010 are proportionally added into high-speed mixer,
Mixing 8 minutes, with banbury banburying 10 minutes after taking-up, last extruding pelletization is standby.
（4）Will be above-mentioned（2）With（3）Standby material carries out melt blending in being added to double screw extruder, and then granulation is obtained
Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet.
（5）Will be above-mentioned（4）Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet as cable
Insulation and restrictive coating, manufacture waterproof flexible cable.
Contrast embodiment：
120 parts of 70 parts of 100 parts of polystyrene-type thermoplastic elastomers SEBS, polypropylene PP, technical white oil 46#, antioxidant
1010 0.5 parts.
（1）SEBS and technical white oil 46# are put into high-speed mixer and mixes oil-filled, mixed 10 minutes, place 36 small
When it is standby.
（2）SEBS, PP and antioxidant after will be oil-filled be put into high-speed mixer, are mixed 10 minutes, are added after taking-up
Melt blending is carried out in being carried out to double screw extruder, then granulation obtains common SEBS/PP thermoplastic elastomer (TPE)s.
Will be above-mentioned（2）Extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material pellet as the exhausted of cable
Edge and restrictive coating, manufacture waterproof flexible cable.
After tested, embodiment 1-3 and protective cover material performance obtained in contrast embodiment are as shown in the table：
Claims (7)
1. a kind of extra large work sea water resistance high intensity high resistance thermoplastic elastomer composite material, it is characterised in that include following
Material, its weight portion is：
100 parts of polystyrene-type thermoplastic elastomers SEBS；
70 ~ 110 parts of polypropylene PP；
100 ~ 120 parts of operation oil；
5 ~ 15 parts of mica powder；
Hexagonal boron nitride nanosheet（BNNS）1 ~ 5 part.
2. a kind of extra large work according to claim 1 sea water resistance high intensity high resistance thermoplastic elastomer composite material, its
It is characterised by, also include auxiliary agent, the auxiliary agent includes following material, and its weight portion is:
0.5 ~ 0.7 part of antioxidant；
0.05 ~ 0.25 part of dispersant；
0.05 ~ 0.15 part of compatilizer.
3. a kind of extra large work according to claim 2 sea water resistance high intensity high resistance thermoplastic elastomer composite material, its
Be characterised by, the compatilizer be 0.05 ~ 0.15 part of titante coupling agent, the dispersant be silane coupler 0.05 ~
0.25 part.
4. a kind of extra large work according to claim 1 sea water resistance high intensity high resistance thermoplastic elastomer composite material, its
It is characterised by, the mica powder is one or more in phlogopite, muscovite and sericite, and particle size range is received for 300 ~ 800
Rice.
5. a kind of extra large work according to claim 1 sea water resistance high intensity high resistance thermoplastic elastomer composite material, its
It is characterised by, the stripping hexagonal boron nitride nanosheet, particle size range is 100 ~ 300 nanometers, 8 ~ 15 nanometers of thickness.
6. a kind of extra large work preparation method of sea water resistance high intensity high resistance thermoplastic elastomer composite material, it is characterised in that
Follow the steps below：
1）BNNS is added in operation oil, then by 4% ~ 7% addition silane coupler of BNNS weight as dispersant, mixing
Use ultrasonic disperser ultrasonic disperse 8 ~ 12 minutes afterwards；
2）The scattered operation oil containing BNNS, the half of antioxidant and SEBS are proportionally added into being mixed in high-speed mixer
Close it is oil-filled, mixing 8 ~ 10 minutes after, place 24 ~ 36 hours, by SEBS fully it is swelling while, BNNS is dispersed in SEBS
Powder surface, then with banbury banburying 10 ~ 15 minutes, last extruding pelletization is standby；
3）By PP, ultrafine mica powder, titanate coupling agent, antioxidant second half be proportionally added into high-speed mixer, mix
Close 8 ~ 12 minutes, with banbury banburying 10 ~ 15 minutes after taking-up, last extruding pelletization is standby；
4）By above-mentioned 2）With 3）Standby material carries out melt blending in being added to double screw extruder, and then granulation obtains composite
Pellet.
7. a kind of extra large work application of sea water resistance high intensity high resistance thermoplastic elastomer composite material, it is characterised in that will make
Insulation and restrictive coating of the standby composite pellet for obtaining as cable, manufacture waterproof flexible cable.
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Cited By (4)
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|---|---|---|---|---|
| CN108102221A (en) * | 2017-12-14 | 2018-06-01 | 义乌倍肯新材料科技有限公司 | A kind of inorganic nano antiseptic thermoplastic elastomer (TPE) and preparation method thereof |
| CN108666014A (en) * | 2018-06-20 | 2018-10-16 | 沈阳天荣电缆材料有限公司 | A kind of sea water resistance semiconductive sealing binding strap and preparation method thereof |
| CN110885653A (en) * | 2019-11-18 | 2020-03-17 | 北京航天控制仪器研究所 | Low-temperature fast-curing epoxy insulating adhesive and preparation method and application thereof |
| CN111995876A (en) * | 2020-07-09 | 2020-11-27 | 上海泛优包装科技有限公司 | Plastic spring material for all-plastic recyclable environment-friendly spray head |
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| 赵迪 等: "氮化硼纳米片制备方法研究进展", 《功能材料》 * |
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| CN108102221A (en) * | 2017-12-14 | 2018-06-01 | 义乌倍肯新材料科技有限公司 | A kind of inorganic nano antiseptic thermoplastic elastomer (TPE) and preparation method thereof |
| CN108666014A (en) * | 2018-06-20 | 2018-10-16 | 沈阳天荣电缆材料有限公司 | A kind of sea water resistance semiconductive sealing binding strap and preparation method thereof |
| CN110885653A (en) * | 2019-11-18 | 2020-03-17 | 北京航天控制仪器研究所 | Low-temperature fast-curing epoxy insulating adhesive and preparation method and application thereof |
| CN110885653B (en) * | 2019-11-18 | 2022-07-05 | 北京航天控制仪器研究所 | Low-temperature fast-curing epoxy insulating adhesive and preparation method and application thereof |
| CN111995876A (en) * | 2020-07-09 | 2020-11-27 | 上海泛优包装科技有限公司 | Plastic spring material for all-plastic recyclable environment-friendly spray head |
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| CN106883618B (en) | 2019-03-12 |
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Effective date of registration: 20200108 Address after: 225652, Beijiao, Jiangsu, Gaoyou province Yangzhou Ling Tong Industrial Park Co-patentee after: Beijing mechanical and electrical engineering general design department Patentee after: Yaguang Cable Co., Ltd., Yangzhou Address before: 225652, Beijiao, Jiangsu, Gaoyou province Yangzhou Ling Tong Industrial Park Patentee before: Yaguang Cable Co., Ltd., Yangzhou |