CN105440412B - 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable - Google Patents
125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable Download PDFInfo
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
Abstract
A kind of 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable of the invention, are grouped as by the group of following parts by weight：20 ~ 25 parts of linear low density polyethylene, 30 ~ 40 parts of metallocene PE, 20 ~ 40 parts of ethylene octene copolymer, 5 ~ 20 parts of ethylene-vinylacetate grafting maleic anhydride copolymer, 90 ~ 110 parts of aluminium hydroxide, 10 ~ 20 parts of ammonium polyphosphate, 1 ~ 4 part of organo montmorillonite, 5 ~ 10 parts of nano-zirconium carbide, 1.2 ~ 1.8 parts of aluminum-zirconium coupling agent, 3 ~ 6 parts of silicone powder, 0.8 ~ 1.5 part of PE waxes, four [β（3,5 di-t-butyl, 4 hydroxy phenyl）Propionic acid] 0.8 ~ 1.2 part of pentaerythrite, 2 ~ 4 parts of 2 MBIZ zinc salt of mercaptobenzimidazole, 1.5 ~ 3 parts of iso-cyanuric acid triallyl ester.The present invention has the characteristics that 125 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin Insulation Materials of the good flame-retardant thin-wall wire for engine of wearability protrusion, high mechanical strength, excellent fireproof performance, low smoke and non-toxic, insulation performance, you can meets the primary insulation for the flame-retardant thin-wall wire for engine that EI105 is required in EN50306 standards for production.
Description
Technical field
The present invention relates to the 125 DEG C of cross-linking radiations in halogen-free flame retardant insulation material field more particularly to a kind of thin-wall locomotive cable
High abrasion halogen-free flame retardant insulation material.
Background technology
With the need of the rapid development of track transportation industry, the appearance of European Union's ROHS and REACH environmental regulation and safety
Want, the requirement to rail traffic cable is also higher and higher, to meet GB/T 12528.11-2004, TJ/CL 254-2013,
The equal rolling stocks specifications of cables of EN 50306 does not require nothing more than safe and environment-friendly Locomotive engine cable, energy saving, high temperature resistant, wear-resisting, Halogen resistance
Combustion, and require to develop to lightweight direction, i.e., flame-retardant thin-wall wire for engine is the Main Trends of The Development of Locomotive engine cable.
Currently, for 125 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin Insulation Materials, early there are research in some domestic producers,
But the relevant criterion requirement of domestic and international Locomotive engine cable should be reached, and need to the product with high mechanical properties and few, Er Qieyong
In the more fewer and fewer of thin wall type locomotive wire.
Invention content
The object of the present invention is to provide a kind of 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulations of thin-wall locomotive cable
Material, 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials have wearability protrusion, high mechanical strength, excellent fireproof performance,
The flame-retardant thin-wall wire for engine of the features such as low smoke and non-toxic, good insulation performance is insulated with 125 DEG C of irradiated crosslinking low-smoke and halogen-free flame retardant polyolefins
Material, you can meet the primary insulation for the flame-retardant thin-wall wire for engine that EI105 is required in EN50306 standards for production.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of 125 DEG C of irradiation of thin-wall locomotive cable
It is crosslinked high abrasion halogen-free flame retardant insulation material, is grouped as by the group of following parts by weight：
20 ~ 25 parts of linear low density polyethylene,
30 ~ 40 parts of metallocene PE,
20 ~ 40 parts of ethylene octene copolymer,
5 ~ 20 parts of maleic anhydride grafted ethene-acetate ethylene copolymer,
90 ~ 110 parts of aluminium hydroxide,
10 ~ 20 parts of ammonium polyphosphate,
1 ~ 4 part of organo montmorillonite,
5 ~ 10 parts of nano-zirconium carbide,
1.2 ~ 1.8 parts of aluminum-zirconium coupling agent,
3 ~ 6 parts of silicone powder,
0.8 ~ 1.5 part of PE waxes,
Four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] 0.8 ~ 1.2 part of pentaerythrite,
2 ~ 4 parts of zinc salt of 2 mercaptobenzimidazole,
1.5 ~ 3 parts of iso-cyanuric acid triallyl ester；
The particle diameter distribution that the nano-zirconium carbide is is 20 ~ 60nm；
The melt index (MI) of the metallocene PE is 0.08 ~ 2g/10min；The melt index (MI) of low density polyethylene (LDPE) be 2 ~
5g/10min；The melt index (MI) of ethylene octene copolymer is 1 ~ 5g/10min；
The grafting rate of the maleic anhydride grafted ethene-acetate ethylene copolymer is 0.6% ~ 1.2%.
The further improved technical solution of above-mentioned technical proposal is as follows：
1. in said program, the aluminum-zirconium coupling agent is the oligomer of the organic complex containing aluminium and zr element, model
For LK-620-1.
2. in said program, the ratio of the aluminum-zirconium coupling agent is nano-zirconium carbide, aluminium hydroxide, ammonium polyphosphate and has
The 1 ~ 1.25% of machine montmorillonite total weight.
3. in said program, the silicone powder be silicone oil and silica proportionally（40~60）：（60~40）Composition.
4. in said program, the organo montmorillonite model SD-2015E.
5. in said program, the four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythrite and 2- sulfydryls
The ratio of benzimidazole zinc salt is 1：（2~4）.
Due to the application of the above technical scheme, the present invention has following advantages compared with prior art：
1. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable of the present invention, using nano silicon carbide
Zirconium is filler, and crystal belongs to NaCl type face-centred cubic structures, the hardness with superelevation, with linear low density polyethylene, highly dense
Degree polyethylene, ethylene octene copolymer and compatilizer are rationally compounded, and nano-zirconium carbide can be prevented directly as hardening constituent
Movement or stablize Grain and sub-grain boundary, limit move dislocation sliding or climb so that material is stronger wear-resistant
Ability.
2. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable of the present invention, using containing aluminium and zirconium
The oligomer of the organic complex of element as coupling agent, can significantly improve aluminium hydroxide, ammonium polyphosphate, organo montmorillonite,
The fillers such as nano-zirconium carbide connect by linear low density polyethylene, metallocene PE, ethylene octene copolymer and maleic anhydride
Dispersibility in the base material system that branch ethylene-vinyl acetate copolymer form according to special ratios, makes material with excellent machine
Tool performance.
3. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable of the present invention, selecting has stratiform
The organo montmorillonite of one-dimensional nano structure is equipped with aluminium hydroxide, ammonium polyphosphate as carbon forming agent, forms inorganic fire-retarded system, both
Good closing layer of charcoal can be formed, and can effectively absorb the hydrogen phosphide of ammonium polyphosphate generation, while inhibiting the generation of hydrogen phosphide.Together
When, as anti-wear additive nano-zirconium carbide due to fusing point it is very high, at a high temperature of combustion process, also can surface formed cause
Close oxide layer, further enhances the crust of material and inorganic fire-retarded system constitutes the effect of cooperative flame retardant, causes material
With preferable flame retardant property, not only can also be burnt by C class bunchys by the single vertical combustion test of IEC standard
Experiment.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment 1 ~ 4：125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of a kind of thin-wall locomotive cable, by following
The group of parts by weight is grouped as, as shown in table 1：
Table 1
The particle diameter distribution that the nano-zirconium carbide is is 20 ~ 60nm；
The melt index (MI) of the metallocene PE is 0.08 ~ 2g/10min；The melt index (MI) of low density polyethylene (LDPE) be 2 ~
5g/10min；The melt index (MI) of ethylene octene copolymer is 1 ~ 5g/10min；
The grafting rate of the maleic anhydride grafted ethene-acetate ethylene copolymer is 0.6% ~ 1.2%.
Above-mentioned aluminum-zirconium coupling agent is the oligomer of the organic complex containing aluminium and zr element, model LK-620-1.
The ratio of above-mentioned aluminum-zirconium coupling agent is nano-zirconium carbide, aluminium hydroxide, ammonium polyphosphate and organo montmorillonite total weight
1 ~ 1.25%.
Above-mentioned organo montmorillonite model SD-2015E.
In embodiment 1 ~ 4, the ratio of aluminum-zirconium coupling agent is that nano-zirconium carbide and aluminium hydroxide, ammonium polyphosphate, organic illiteracy are de-
The accounting of native total weight is followed successively by：Embodiment 1 is 1.08%, embodiment 1 is 1.06%, embodiment 3 is 1.0%, embodiment 4 is
1.18%。
In embodiment 1 ~ 4, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythrite and 2- sulfydryl benzo miaows
The ratio of azoles zinc salt is followed successively by：Embodiment 1 is 1：2.2, embodiment 2 is 1：3, embodiment 3 is 1：3.5, embodiment 4 is 1：2.
A kind of preparation side for 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of above-mentioned thin-wall locomotive cable
Method includes the following steps：
The first step：By 20 ~ 25 parts of the linear low density polyethylene measured by formulation weight, 30 ~ 40 parts of metallocene PE,
20 ~ 40 parts of ethylene octene copolymer, 5 ~ 20 parts of maleic anhydride grafted ethene-acetate ethylene copolymer are high in high-speed mixer
Speed mixing 30 seconds mixes plasticizing through dual-screw pelletizer and is granulated.Processing temperature is：120~130 DEG C of transportation section, melt zone 140
~155 DEG C, 160~170 DEG C of mixing section, 155~165 DEG C of exhaust section, 155~165 DEG C of homogenizing zone, 160~170 DEG C of head；
Second step：90 ~ 110 parts of the aluminium hydroxide by formulation weight metering, ammonium polyphosphate 10 ~ 20 is added in above-mentioned material
Part, 1 ~ 4 part of organo montmorillonite, 5 ~ 10 parts of nano-zirconium carbide, 1.2 ~ 1.8 parts of aluminum-zirconium coupling agent, 3 ~ 6 parts of silicone powder, PE waxes 0.8 ~
1.5 parts, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] 0.8 ~ 1.2 part of pentaerythrite, zinc salt of 2 mercaptobenzimidazole
2 ~ 4 parts and 1.5 ~ 3 parts of iso-cyanuric acid triallyl ester, mix 30 seconds, then mediated in double rank machines in high-speed mixer
Plasticizing is granulated.Double rank machines include twin-screw and single screw rod, and the processing temperature of wherein twin-screw is：100~115 DEG C of transportation section is melted
Melt 120~135 DEG C of section, 140~150 DEG C of mixing section, 145~155 DEG C of exhaust section, 145~155 DEG C of homogenizing zone, head 150~
160℃；Single screw rod processing temperature is：First 120~135 DEG C of area, the second 120~135 DEG C of area, 120~135 DEG C of third area, machine
First 130~145 DEG C, packaging after pelletizing is air-cooled；
Third walks：Second step resulting materials are squeezed in electric wire on line machine production line, 120~130 DEG C of an area, 2nd area
130~145 DEG C, three 145~165 DEG C of areas, four 145~165 DEG C of areas squeeze out at a temperature of 150~160 DEG C of head, are coated on and lead
On body core, then irradiation processing is carried out, heat extends 15%~30% after irradiation.
The property of 125 DEG C of cross-linking radiation high abrasion non-halogen flame-retardant cables of thin-wall locomotive cable obtained by embodiment 1 ~ 4
Energy test data is as shown in table 2：
Table 2
The thin-wall locomotive cable of 1 ~ 4 gained of embodiment is used as with 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials
Cross-sectional area of conductor is 0.75mm2, wall thickness be 0.18mm electric wire test performance result it is as shown in table 3 below：
Table 3
Performance can be seen that thin-wall locomotive cable of the present invention with 125 DEG C of cross-linking radiation high abrasion halogen-free flameproofs from table 2 ~ 3
Insulation Material is connect using the linear low density polyethylene of special parameter, metallocene PE, ethylene octene copolymer and maleic anhydride
Branch ethylene-vinyl acetate copolymer is mixed with nano-zirconium carbide, aluminium hydroxide, ammonium polyphosphate, organo montmorillonite as basis material
It closes, and is furnished with specific aluminum-zirconium coupling agent and lubricant, with higher mechanical strength, low smoke and non-toxic and excellent wear-resisting
Performance, anti-flammability and insulation performance etc. can be used for producing the internal layer for the thin wall type locomotive cable for meeting the requirement of EN50306 standards
Insulation.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable, it is characterised in that：By following heavy
The group of amount part is grouped as：
20 ~ 25 parts of linear low density polyethylene,
30 ~ 40 parts of metallocene PE,
20 ~ 40 parts of ethylene octene copolymer,
5 ~ 20 parts of maleic anhydride grafted ethene-acetate ethylene copolymer,
90 ~ 110 parts of aluminium hydroxide,
10 ~ 20 parts of ammonium polyphosphate,
1 ~ 4 part of organo montmorillonite,
5 ~ 10 parts of nano-zirconium carbide,
1.2 ~ 1.8 parts of aluminum-zirconium coupling agent,
3 ~ 6 parts of silicone powder,
0.8 ~ 1.5 part of PE waxes,
Four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] 0.8 ~ 1.2 part of pentaerythritol ester,
2 ~ 4 parts of zinc salt of 2 mercaptobenzimidazole,
1.5 ~ 3 parts of iso-cyanuric acid triallyl ester；
The particle size distribution of the nano-zirconium carbide is 20 ~ 60nm；
The melt index (MI) of the metallocene PE is 0.08 ~ 2g/10min；The melt index (MI) of linear low density polyethylene be 2 ~
5g/10min；The melt index (MI) of ethylene octene copolymer is 1 ~ 5g/10min；
The grafting rate of the maleic anhydride grafted ethene-acetate ethylene copolymer is 0.6% ~ 1.2%.
2. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable according to claim 1, special
Sign is：The aluminum-zirconium coupling agent is the oligomer of the organic complex containing aluminium and zr element, model LK-620-1.
3. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable according to claim 1, special
Sign is：The ratio of the aluminum-zirconium coupling agent is nano-zirconium carbide, aluminium hydroxide, ammonium polyphosphate and organo montmorillonite total weight
1~1.25%。
4. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable according to claim 1, special
Sign is：The silicone powder be silicone oil and silica proportionally（40~60）：（60~40）Composition.
5. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable according to claim 1, special
Sign is：The organo montmorillonite model SD-2015E.
6. 125 DEG C of cross-linking radiation high abrasion halogen-free flame retardant insulation materials of thin-wall locomotive cable according to claim 1, special
Sign is：Four [the β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythrite and zinc salt of 2 mercaptobenzimidazole
Ratio is 1：（2~4）.
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| CN104004264A (en) * | 2014-06-13 | 2014-08-27 | 浙江万马高分子材料有限公司 | Inflaming retarding polyolefin cable material and preparing method and application thereof |
| CN104441852A (en) * | 2014-12-10 | 2015-03-25 | 平顶山华瑞锦橡耐磨材料有限公司 | Layered wear-erosion resistant rubber lining plate and preparation method thereof |
| CN104650449A (en) * | 2015-02-13 | 2015-05-27 | 深圳市沃尔核材股份有限公司 | Halogen-free and antimony-free flame-retardant cable material with resistant temperature of 125 DEG C and production method of cables |
| CN105086276A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | High-abrasion-resistance modified PVC (polyvinyl chloride) wood-plastic material |
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Effective date of registration: 20201106 Address after: No.6, HuaSu West Road, taicanggang economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee after: CGN DELTA (JIANGSU) PLASTICS Co.,Ltd. Address before: 215433 Jiangsu city in Suzhou Province, visit the home town of Taicang City North First Patentee before: CGN-DELTA (SUZHOU) POLYMER Co.,Ltd. |