CN106700561A - Halogen-free flame-retardant sheath material for soft wear-resistant oil-resistant irradiation crosslinking locomotive cable - Google Patents
Halogen-free flame-retardant sheath material for soft wear-resistant oil-resistant irradiation crosslinking locomotive cable Download PDFInfo
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- CN106700561A CN106700561A CN201611021467.XA CN201611021467A CN106700561A CN 106700561 A CN106700561 A CN 106700561A CN 201611021467 A CN201611021467 A CN 201611021467A CN 106700561 A CN106700561 A CN 106700561A
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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
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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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
- H01B3/307—Other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Insulated Conductors (AREA)
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Abstract
The invention discloses a halogen-free flame-retardant sheath material for a soft wear-resistant oil-resistant irradiation crosslinking locomotive cable. The halogen-free flame-retardant sheath material for the locomotive cable consists of the following components: linear low-density polyethylene, ethylene-vinyl acetate copolymer, EVA-g-PU copolymer, maleic anhydride grafted ethylene-propylene terpolymer, hydroxyl-terminated hyper-branched polyester, organic nano montmorillonite, aluminum hydroxide, vinyl-tris(2-methoxyethoxy) silane, melamine cyanurate, silicone oil, zinc stearate, triallyl isocyanurate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, dilauryl thiodipropionate and diphenylamine (5057) containing butyl and octyl. In the EVA-g-PU copolymer, the weight content of VA (vinyl acetate) of comonomer EVA (ethylene-vinyl acetate) is 28%, and the PU (polyurethane) is polyether type polyurethane prepolymer and has a weight content of 5-10%. The flexibility and wear resistance of the halogen-free flame-retardant sheath material are improved; and while good compatibility with other base materials is ensured, the low-temperature flexibility and oil resistance of the material are improved.
Description
Technical field
The present invention relates to non-halogen flame-retardant cable technical field, more particularly to a kind of locomotive cable halogen-free flameproof sheath
Material.
Background technology
With the need of the developing rapidly of track transportation industry, the appearance of European Union's ROHS and REACH environmental regulation and safety
Will, requirement to track traffic cable also more and more higher, to meet GB/T 12528.11-2004, TJ/CL 254-2013,
The grade rolling stock specifications of cables of EN 50306, does not require nothing more than that Locomotive engine cable is safe and environment-friendly, energy-conservation, to oil resistant, high-low temperature resistant, resistance to
The requirement also more and more higher of mill and fire resistance, in addition, it is contemplated that cable facilitates problem in laid processes, to the soft of material
It is soft to there has also been certain requirement.
In published Chinese patent literature, the technical information of the non-halogen flame-retardant cable of oil-resisting type is a lot, but
The relevant report that soft, wear-resisting, fire-retardant and oil resistance polyolefine material can simultaneously be taken into account is little, such as CN
101445630A：The cable material and preparation method of the special softness oil-proof rubber elastomer of high intensity, using material based on EVA,
But need sulfidation；CN 201514804U novel high-voltage direct-current cable for locomotive, the material for using has soft and oil resistivity
Can, main base material is ethylene propylene diene rubber, needs also exist for sulfidation；CN 104672743A：A kind of corrosion-resistant super softness of oil resistant
Cable jacket material and preparation method thereof, it is common using styrene-ethylene-butylene-styrene block copolymer, propylene-ethylene-octene
Material based on polymers etc..
So, conventional low-smoke halide-free fireproof composite polyolefine material is extremely difficult to oil resistant and soft, wear-resisting requirement in performance
Balance, while also need by the single vertical combustion test of IEC60332-1, there is certain difficulty in prior art.Such as
Fruit overcomes above-mentioned technical problem, as the direction that those of ordinary skill in the art make great efforts.
The content of the invention
It is an object of the invention to provide a kind of soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material, should
Locomotive cable Halogen-free flame retardant sheath material improves the compliance and anti-wear performance of Halogen-free flame retardant sheath material；Ensure that and other
While base material good compatibility, the low-temperature flexibility and low temperature oil resistance of material are also improved.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of soft abrasion-resistant oil resistant radiation crosslinking machine
Car cable Halogen-free flame retardant sheath material, the locomotive cable Halogen-free flame retardant sheath material is made up of the component of following weight portion：
10 ~ 25 parts of LLDPE,
15 ~ 25 parts of ethylene-vinyl acetate copolymer,
30 ~ 50 parts of EVA-g-PU copolymers,
Maleic anhydride is grafted 10 ~ 25 parts of ternary ethylene-propylene copolymer,
5 ~ 10 parts of superbrnaching end-hydroxy polyester,
3 ~ 10 parts of nano imvite,
90 ~ 130 parts of aluminium hydroxide,
0.8 ~ 1.2 part of vinyl-three (2- methoxy ethoxies) silane,
5 ~ 20 parts of MCA,
0.5 ~ 2 part of silicone oil,
0.5 ~ 2 part of zinc stearate,
1.5 ~ 2.5 parts of Triallyl isocyanurate,
It is double（3,5- di-t-butyl -4- hydroxy benzenes propionyl）0.8 ~ 1.2 part of hydrazine,
Double 0.5 ~ 2 part of the lauryls of thio-2 acid,
Diphenylamines containing butyl and octyl group（5057）0.5 ~ 2 part；
In the EVA-g-PU copolymers, the VA weight contents of comonomer EVA are Polyether-Polyol Polyurethane Prepolymer for 28%, PU,
PU performed polymers weight content is 5 ~ 10%；
The melt index (MI) of the LLDPE is 2 ~ 5g/10min；
The superbrnaching end-hydroxy polyester has long-Chain aromatic adoption ester structure, and molecular weight is 500 ~ 5000g/mol, and hydroxyl value is
5~50/mol。
The further improved technical scheme of above-mentioned technical proposal is as follows：
1. in such scheme, the vinylacetate percentage composition of the ethylene-vinyl acetate copolymer for mass fraction 28 ~
50%。
2. in such scheme, the grafting rate of the maleic anhydride grafting ternary ethylene-propylene copolymer is 0.8 ~ 2.0%.
3. it is described double in such scheme（3,5- di-t-butyl -4- hydroxy benzenes propionyl）The double lauryls of hydrazine, thio-2 acid
With the diphenylamines containing butyl and octyl group（5057）Ratio be 1：（0.5~1.2）：（0.5~1）.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art：
1. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of the invention, poly- using linea low density
10 ~ 25 parts of ethene, 15 ~ 25 parts of ethylene-vinyl acetate copolymer, 30 ~ 50 parts of EVA-g-PU copolymers, maleic anhydride grafting three
The specific copolymer melt blending of four kinds of first ethylene-propylene copolymer 10 ~ 25 part, and superbrnaching end-hydroxy polyester is equipped with, improve Halogen
The compliance and anti-wear performance of flame-retardant sheath material；Secondly, in its EVA-g-PU copolymer, the VA weight contents of comonomer EVA
It is that 28%, PU is Polyether-Polyol Polyurethane Prepolymer, its weight content is 5 ~ 10%, ensure that the compatibility good with other base materials
While, also improve the low-temperature flexibility and oil resistance of material.
2. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of the invention, its EVA-g-PU is total to
Polymers and the synergy of superbrnaching end-hydroxy polyester, are equipped with silicone oil, zinc stearate, and not only compatibility is good, improve the molten of base material
Liquid flowability, moreover it is possible to reduce processing electric current and temperature, improves processing characteristics；Again, its EVA-g-PU copolymer surpasses with terminal hydroxy group
Branched polyester synergy is equipped with organic nano imvite, aluminium hydroxide and MCA, hyperbranched poly ester molecule
Terminal hydroxy group in structure, the hydroxyl with nano imvite surface forms hydrogen bond, suppresses to reunite, and improves dispersiveness, further improves
The anti-wear performance of material, fire resistance and tensile property.
3. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of the invention, it is low close that it is used
Degree polyethylene, ethylene-vinyl acetate copolymer, EVA-g-PU copolymers, maleic anhydride four kinds of ternary ethylene-propylene copolymer of grafting
Specific base material, is equipped with double（3,5- di-t-butyl -4- hydroxy benzenes propionyl）The double lauryls of hydrazine, thio-2 acid and contain butyl and pungent
The antioxidant system of the diphenylamines composition of base, in the processing stability of reinforcing material, improves on the basis of thermal-oxidative aging property, more has
What is imitated ensure that its oil resistance.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1 ~ 5：A kind of soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material, the locomotive cable is used
Halogen-free flame retardant sheath material is made up of the component of following weight portion：As shown in table 1：
Table 1
In above-described embodiment 1 ~ 5, the melt index (MI) of the LLDPE is 4g/10min；The maleic anhydride grafting
The grafting rate of ternary ethylene-propylene copolymer is 0.8%；In EVA-g-PU copolymers, the VA weight contents of comonomer EVA are 28%.
Wherein, in embodiment 1, the PU performed polymers weight content of described EVA-g-PU copolymers is 5%, described end hydroxyl
The hydroxyl value of base hyper-branched polyester is 10 ~ 12/mol, and molecular weight is 1100g/mol, the ethylene-vinyl acetate copolymer
VA weight contents are 28%.
In embodiment 2, the PU performed polymers weight content 10% of described EVA-g-PU copolymers, described terminal hydroxy group over-expense
The hydroxyl value for changing polyester is 20 ~ 24/mol, and molecular weight is 2400g/mol, the VA weight of the ethylene-vinyl acetate copolymer
Content is 33%.
In embodiment 3, the PU performed polymers weight content 7% of described EVA-g-PU copolymers, described superbrnaching end-hydroxy
The hydroxyl value of polyester is 5 ~ 7/mol, and molecular weight is 500g/mol, the VA weight contents of the ethylene-vinyl acetate copolymer
It is 33%.
In embodiment 4, the PU performed polymer weight contents of described EVA-g-PU copolymers are respectively 7%；Described terminal hydroxy group
The hydroxyl value of hyper-branched polyester is 10 ~ 12/mol, and molecular weight is 1100g/mol, the VA of the ethylene-vinyl acetate copolymer
Weight content is 40%.
In embodiment 5, the PU performed polymer weight contents of described EVA-g-PU copolymers are respectively 5%；Described terminal hydroxy group
The hydroxyl value of hyper-branched polyester is 20 ~ 24/mol, and molecular weight is 2400g/mol, the VA of the ethylene-vinyl acetate copolymer
Weight content is 28%.
One kind is for the soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of above-described embodiment 1 ~ 5
Preparation method, comprises the following steps：
Step one, the LLDPE by the composition of raw materials of CABLE MATERIALS, ethylene-vinyl acetate copolymer, EVA-
G-PU copolymers, maleic anhydride grafting ternary ethylene-propylene copolymer, superbrnaching end-hydroxy polyester, organic nano imvite, hydroxide
Aluminium, vinyl-three (2- methoxy ethoxies) silane, MCA, silicone oil, zinc stearate, triallyl isocyanide
It is urea acid esters, double（3,5- di-t-butyl -4- hydroxy benzenes propionyl）The double lauryls and containing butyl and octyl group two of hydrazine, thio-2 acid
Aniline（5057）, weighed according to parts by weight, it is that 5 ~ 10min is stirred in 60 ~ 80 DEG C of high-speed mixer to be put into temperature, it is uniform after
Discharging, through the adding pressure type mixer mixing that temperature is 130 ~ 140 DEG C；Then the twin-screw that extrusion temperature is 110 ~ 150 DEG C is used
Extruder extruding pelletization is simultaneously dried, you can obtaining can cross-linking radiation low-temperature resistant soft oil resistant non-halogen flame-retardant cable.
Step 2, pellet is plastified on a mill, slice, the mill temperature be 130 ~ 145 DEG C；Gained sheet stock is put
6min is preheated in 160 ~ 170 DEG C of hydraulic presses, then pressurized, heated 4min, pressure is more than 15MPa, repressurization is cooled to room temperature.
It is step 3, last, test piece is carried out into cross-linking radiation, irradiation dose is 15 ~ 18Mard, and heat extends control 5 ~ 30%.
The performance of the soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material obtained by embodiment 1 ~ 3 is surveyed
Examination data, as shown in table 2：
Table 2
Performance can be seen that soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of the invention from table 2,
Excellent with soft, anti-wear performance, surface is not likely to produce scratch or rupture in use, and oil resistance is protruded, resistance to
Low temperature, fire resistance are good, LSZH the features such as, can be used for producing the oil resistant locomotive cable for meeting GB, Europe superscript requirement.Always
It, soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material of the invention, with oil resistance protrude, it is soft
Soft, anti-wear performance is excellent, fire resistance is good, LSZH the features such as, can be used for producing and meet GB, the oil resistant of Europe superscript requirement
Locomotive cable.
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (4)
1. a kind of soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material, it is characterised in that：The locomotive electricity
Cable Halogen-free flame retardant sheath material is made up of the component of following weight portion：
10 ~ 25 parts of LLDPE,
15 ~ 25 parts of ethylene-vinyl acetate copolymer,
30 ~ 50 parts of EVA-g-PU copolymers,
Maleic anhydride is grafted 10 ~ 25 parts of ternary ethylene-propylene copolymer,
5 ~ 10 parts of superbrnaching end-hydroxy polyester,
3 ~ 10 parts of nano imvite,
90 ~ 130 parts of aluminium hydroxide,
0.8 ~ 1.2 part of vinyl-three (2- methoxy ethoxies) silane,
5 ~ 20 parts of MCA,
0.5 ~ 2 part of silicone oil,
0.5 ~ 2 part of zinc stearate,
1.5 ~ 2.5 parts of Triallyl isocyanurate,
It is double（3,5- di-t-butyl -4- hydroxy benzenes propionyl）0.8 ~ 1.2 part of hydrazine,
Double 0.5 ~ 2 part of the lauryls of thio-2 acid,
Diphenylamines containing butyl and octyl group（5057）0.5 ~ 2 part；
In the EVA-g-PU copolymers, the VA weight contents of comonomer EVA are Polyether-Polyol Polyurethane Prepolymer for 28%, PU,
PU performed polymers weight content is 5 ~ 10%；
The melt index (MI) of the LLDPE is 2 ~ 5g/10min；
The superbrnaching end-hydroxy polyester has long-Chain aromatic adoption ester structure, and molecular weight is 500 ~ 5000g/mol, and hydroxyl value is
5~50/mol。
2. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material according to claim 1, its feature
It is：The vinylacetate percentage composition of the ethylene-vinyl acetate copolymer is mass fraction 28 ~ 50%.
3. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material according to claim 1, its feature
It is：The grafting rate of the maleic anhydride grafting ternary ethylene-propylene copolymer is 0.8 ~ 2.0%.
4. soft abrasion-resistant oil resistant cross-linking radiation locomotive cable Halogen-free flame retardant sheath material according to claim 1, its feature
It is：It is described double（3,5- di-t-butyl -4- hydroxy benzenes propionyl）The double lauryls of hydrazine, thio-2 acid with containing butyl and octyl group
Diphenylamines（5057）Ratio be 1：（0.5~1.2）：（0.5~1）.
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Cited By (5)
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| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
| CN112608585A (en) * | 2020-12-10 | 2021-04-06 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN114141430A (en) * | 2019-06-20 | 2022-03-04 | 广西纵览线缆集团有限公司 | Manufacturing process of low-shrinkage composite cable |
| CN114163705A (en) * | 2021-12-31 | 2022-03-11 | 深圳先进电子材料国际创新研究院 | Polyolefin-based flame-retardant heat conduction material and preparation method and application thereof |
| CN116355310A (en) * | 2023-04-23 | 2023-06-30 | 金发科技股份有限公司 | Flame-retardant semiconductive shielding material and preparation method and application thereof |
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Cited By (8)
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| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
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| CN112608585A (en) * | 2020-12-10 | 2021-04-06 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN112608585B (en) * | 2020-12-10 | 2022-12-30 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN114163705A (en) * | 2021-12-31 | 2022-03-11 | 深圳先进电子材料国际创新研究院 | Polyolefin-based flame-retardant heat conduction material and preparation method and application thereof |
| CN114163705B (en) * | 2021-12-31 | 2024-01-23 | 深圳先进电子材料国际创新研究院 | Polyolefin-based flame-retardant heat conduction material and preparation method and application thereof |
| CN116355310A (en) * | 2023-04-23 | 2023-06-30 | 金发科技股份有限公司 | Flame-retardant semiconductive shielding material and preparation method and application thereof |
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