CN109575499A - A kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible - Google Patents
A kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible Download PDFInfo
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- CN109575499A CN109575499A CN201811301490.3A CN201811301490A CN109575499A CN 109575499 A CN109575499 A CN 109575499A CN 201811301490 A CN201811301490 A CN 201811301490A CN 109575499 A CN109575499 A CN 109575499A
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
A kind of high-elastic resistance to voltage cable of new-energy automobile highly-flexible, including center conductor, crosslinking TPE insulating layer, protective layer, shielded layer and crosslinking TPE restrictive coating；Center conductor is to be formed by annealing naked copper or tin plating stranded conductor by intersecting regular be twisted；The periphery of center conductor closely coats crosslinking TPE insulating layer, and the periphery of crosslinking TPE insulating layer is closely coated with protective layer, and the periphery of protective layer is closely coated with shielded layer, and the periphery of shielded layer closely coats crosslinking TPE restrictive coating.The present invention overcomes cable existing problem of Cracking in long-term use, and guarantee the high flexibility that cable uses, while guaranteeing that cable can satisfy 1.5kv or higher voltage rating, have both the performance advantage of general T PE insulated cable and XLPE insulated cable.
Description
Technical field
The present invention relates to the technical fields of new energy cable material, and in particular to a kind of new-energy automobile highly-flexible is high-elastic
The crosslinking TPE material of resistance to voltage cable.
Background technique
In the high-tension cable of new-energy automobile, the insulating layer and jacket layer material that early period selects are mainly TPE material
(thermoplastic elastic material), this material are not necessarily to cross-linking radiation, and with the advantage in production efficiency, but such material is mainly deposited
In the problem of Cracking of long-time service.The material that later period selects is mainly XLPE composite materials (cross-linking polyethylene materials), but
There are disadvantages in terms of hardness and elasticity for XLPE material, and pliability is bad in big squares lead.
In conclusion conventional new energy conducting wire has the disadvantage that one, tensile strength is poor currently on the market, it is universal small
In 10Mpa；Two, hardness is insufficient, only 85A or so；Three, intensity is low and pliability is poor, causes bending radius excessive.
Therefore, above-mentioned the shortcomings of the prior art how is solved, is become as the project of the invention to be researched and solved.
Summary of the invention
It is an object of the present invention to provide a kind of crosslinking TPE materials of automobile-used high-elastic resistance to voltage cable of highly-flexible.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible, for the insulating layer or/and sheath of the cable to be made
Layer；
The raw material of the crosslinking TPE material comprises the following components in parts by weight:
25 ~ 35 parts of SEBS；
20 ~ 30 parts of polypropylene；
20 ~ 30 parts of phosphorus-nitrogen containing flame retardant；
5 ~ 10 parts of nano silica；
5 ~ 15 parts of naphthenic oil；
5 ~ 10 parts of crosslinking agent；
2 ~ 5 parts of lubricant；
2 ~ 3 parts of Masterbatch；
0.2 ~ 1 part of antioxidant；
The preparation process of the crosslinking TPE material is as follows:
Firstly, SEBS and naphthenic oil are stirred in low-speed mixer, mixing time is 2 ~ 4min, makes the abundant oil suction of SEBS
Swelling；
Then, polypropylene is added, continues to stir 2min, nano silica, fire retardant, lubricant, crosslinking agent, color is then added
Masterbatch, antioxidant, and 5 ~ 10min is stirred in high-speed mixer, obtain the homogeneous mixture of the crosslinking TPE material；
Finally, melt blending, processing temperature are 180 ~ 210 DEG C in double screw extruder by the mixture, material strip is squeezed out, with
Stretching and granulation afterwards；
Preliminary drying dry-cure is carried out to the crosslinking TPE material when cable squeezes out, drying temperature is 80 ~ 100 DEG C, drying time for 4 ~
The temperature of 6h, extrusion are controlled at 180 ~ 200 DEG C；
Cable is irradiated after the completion of squeezing out, and the irradiation dose of material is 12 ~ 17Mard/mm, and the heat of insulating layer and restrictive coating is prolonged
Control is stretched 40 ~ 70%.
Related content in above-mentioned technical proposal is explained as follows:
1, in above scheme, SEBS is to be copolymerized using polystyrene as end segment with the Ethylene/Butylene that polybutadiene plus hydrogen obtain
Object is the linear tri-block copolymer of intermediate elastic block.
By the way that crosslinking agent is added in TPE material, can make in material after through gamma-rays or electron beam irradiation
SEBS material is crosslinked, and material can be enhanced after irradiation with the speed of 20 ~ 40m/min by radiation source in cable when irradiation
Performance.
SEBS and polypropylene are the main component of TPE material, by adjusting the proportion adjustable material of two class materials
The elongation and rubber feel of material can be improved in final feel and tensile strength and elongation, the content for improving SEBS；It improves
Polypropylene content can be improved the strength of materials, and the weight ratio of usual polypropylene and SEBS are 1:1.5 ~ 1:2.2.
2, in above scheme, the component of the preferably following parts by weight of raw material of the crosslinking TPE material:
27 ~ 34 parts of SEBS；
23 ~ 29 parts of polypropylene；
21.5 ~ 28 parts of phosphorus-nitrogen containing flame retardant；
6 ~ 8.5 parts of nano silica；
8 ~ 12 parts of naphthenic oil；
5.5 ~ 9.5 parts of crosslinking agent；
2.2 ~ 4.3 parts of lubricant；
2.1 ~ 2.8 parts of Masterbatch；
0.35 ~ 0.85 part of antioxidant.
3, in above scheme, the polyacrylic melt index is 0.8 ~ 2g/10min.
4, in above scheme, the flash-point of the naphthenic oil is greater than 170 DEG C, and saturated hydrocarbon content therein be 89.2 ~
94.0%.The adjustable material hardness of naphthenic oil meets requirement of the cable to hardness.
5, in above scheme, the phosphorus-nitrogen containing flame retardant is formed using polyol, the polyol packet
Include following one or more of ingredients:
Pentaerythrite, ammonium polyphosphate, melamine.
It designs whereby, can react to each other in flame environment and form layer of charcoal on the surface of cable, prevent and air is after continued access
Touching, reaches flame retardant effect.
6, in above scheme, the crosslinking agent uses TAIC(Triallyl isocyanurate), preparing the crosslinking TPE
Before material, TAIC first passes through coupling agent and is surface-treated；
The coupling agent is aminopropyl triethoxysilane, and parts by weight used are the 5 ~ 10% of the crosslinking agent；
The method of the surface treatment is that in high-speed mixer, (no specific mixing speed is wanted with the coupling agent by the crosslinking agent
Ask, use conventional high-speed mixer) in be stirred 2 ~ 5min of mixing, until material is in uniformed powder shape and without particle；
It is passed through 110 ~ 120 DEG C of hot-air after the completion of mixing and dries 3 ~ 5min, is cooled to 20 ~ 35 DEG C.
By adding crosslinking agent, the SEBS being crosslinked in TPE material crosslinking can be made after electron beam irradiation, it is adjacent
Two free radical couplings of SEBS, form cross-bond, improve the heat resistance, flame resistance and mechanical strength of material.
Coupling agent can guarantee the evenly dispersed of crosslinking agent, guarantee that cable irradiation is uniform.
7, in above scheme, cable is irradiated after the completion of squeezing out, and the irradiation dose of material is 12 ~ 17Mard/mm, to prevent
Only cross irradiation and irradiation not exclusively, specific irradiation dose is regulated and controled according to the thickness of cable；The heat of insulating layer and restrictive coating is prolonged
Control is stretched 40 ~ 70%.
The hardness of the crosslinking TPE material is 80A, and soft, elasticity is good.
The crosslinking TPE material has the advantages that TPE and XLPE(crosslinked polyethylene), it can be improved the stabilization of cable operation
Property and anti-cracking performance, and it is able to satisfy 125 DEG C and 150 DEG C of use temperature.
The working principle of the invention and advantage are as follows:
Compared to existing technologies, the flexibility and installability of cable entirety can be improved in the present invention.
The present invention is crosslinked the insulating layer and restrictive coating that TPE material is used for cable, therefore cable can be made to have excellent anti-tensile
Intensity, elongation at break, tearing strength.By being cross-linked to form reticular structure between material molecule, long-time service is not in cracking,
Compared to having high-flexibility and elastomeric advantage for XLPE material, conducive to the cable laying requirement of small-bend radius.
To sum up, the present invention overcomes cable existing problem of Cracking in long-term use, and guarantee the Gao Rou that cable uses
It is soft, while guaranteeing that cable can satisfy 1.5kv or higher voltage rating, have both general T PE insulated cable and XLPE insulation
The performance advantage of cable.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment: a kind of crosslinking TPE material of the automobile-used high-elastic resistance to voltage cable of highly-flexible, for the insulating layer of the cable to be made
Or/and restrictive coating；
The raw material of the crosslinking TPE material comprises the following components in parts by weight:
25 ~ 35 parts of SEBS；
20 ~ 30 parts of polypropylene；
20 ~ 30 parts of phosphorus-nitrogen containing flame retardant；
5 ~ 10 parts of nano silica；
5 ~ 15 parts of naphthenic oil；
5 ~ 10 parts of crosslinking agent；
2 ~ 5 parts of lubricant；
2 ~ 3 parts of Masterbatch；
0.2 ~ 1 part of antioxidant.
SEBS is using polystyrene as end segment, and the ethylene-butene copolymer obtained with polybutadiene plus hydrogen is intermediate bullet
The linear tri-block copolymer of property block.
By the way that crosslinking agent is added in TPE material, can make in material after through gamma-rays or electron beam irradiation
SEBS material is crosslinked, and material can be enhanced after irradiation with the speed of 20 ~ 40m/min by radiation source in cable when irradiation
Performance.
SEBS and polypropylene are the main component of TPE material, by adjusting the proportion adjustable material of two class materials
The elongation and rubber feel of material can be improved in final feel and tensile strength and elongation, the content for improving SEBS；It improves
Polypropylene content can be improved the strength of materials, and the weight ratio of usual polypropylene and SEBS are 1:1.5 ~ 1:2.2.
The component of the preferably following parts by weight of raw material of the crosslinking TPE material:
27 ~ 34 parts of SEBS；
23 ~ 29 parts of polypropylene；
21.5 ~ 28 parts of phosphorus-nitrogen containing flame retardant；
6 ~ 8.5 parts of nano silica；
8 ~ 12 parts of naphthenic oil；
5.5 ~ 9.5 parts of crosslinking agent；
2.2 ~ 4.3 parts of lubricant；
2.1 ~ 2.8 parts of Masterbatch；
0.35 ~ 0.85 part of antioxidant.
Wherein, the polyacrylic melt index is 0.8 ~ 2g/10min.
The flash-point of the naphthenic oil is greater than 170 DEG C, and saturated hydrocarbon content therein is 89.2 ~ 94.0%.Naphthenic oil can be adjusted
Whole material hardness meets requirement of the cable to hardness.
The phosphorus-nitrogen containing flame retardant is formed using polyol, and the polyol includes following a kind of or several
Kind ingredient:
Pentaerythrite, ammonium polyphosphate, melamine.
It designs whereby, can react to each other in flame environment and form layer of charcoal on the surface of cable, prevent and air is after continued access
Touching, reaches flame retardant effect.
More preferably, the raw material of the crosslinking TPE material comprises the following components in parts by weight:
31 parts of SEBS；
Polipropene 25 part；
26.5 parts of phosphorus-nitrogen containing flame retardant；
7.2 parts of nano silica；
9.5 parts of naphthenic oil；
7.5 parts of crosslinking agent；
3.3 parts of lubricant；
2.5 parts of Masterbatch；
0.65 part of antioxidant.
Wherein, the crosslinking agent uses TAIC(Triallyl isocyanurate), before preparing the crosslinking TPE material,
TAIC first passes through coupling agent and is surface-treated；
The coupling agent is aminopropyl triethoxysilane, and parts by weight used are the 5 ~ 10% of the crosslinking agent；
The method of the surface treatment is that in high-speed mixer, (no specific mixing speed is wanted with the coupling agent by the crosslinking agent
Ask, use conventional high-speed mixer) in be stirred 2 ~ 5min of mixing, until material is in uniformed powder shape and without particle；
It is passed through 110 ~ 120 DEG C of hot-air after the completion of mixing and dries 3 ~ 5min, is cooled to 20 ~ 35 DEG C.
By adding crosslinking agent, the SEBS being crosslinked in TPE material crosslinking can be made after electron beam irradiation, it is adjacent
Two free radical couplings of SEBS, form cross-bond, improve the heat resistance, flame resistance and mechanical strength of material.
Coupling agent can guarantee the evenly dispersed of crosslinking agent, guarantee that cable irradiation is uniform.
Wherein, the preparation process of the crosslinking TPE material is as follows:
Firstly, by SEBS and naphthenic oil, in low-speed mixer, (no specific mixing speed is required, and is using conventional low-speed mixer
Can) in be stirred, mixing time is 2 ~ 4min, makes SEBS abundant oil suction swelling；
Then, polypropylene is added, continues to stir 2min, nano silica, fire retardant, lubricant, crosslinking agent, color is then added
Masterbatch, antioxidant, and 5 ~ 10min is stirred in high-speed mixer, obtain the homogeneous mixture of the crosslinking TPE material；
Finally, melt blending, processing temperature are 180 ~ 210 DEG C in double screw extruder by the mixture, material strip is squeezed out, with
Stretching and granulation afterwards.
Wherein, preliminary drying dry-cure is carried out to the crosslinking TPE material when cable squeezes out, drying temperature is 80 ~ 100 DEG C, is dried
The dry time is 4 ~ 6h, and the temperature of extrusion is controlled at 180 ~ 200 DEG C；
Cable is irradiated after the completion of squeezing out, and the irradiation dose of material is 12 ~ 17Mard/mm, to prevent from irradiating and irradiate not
Completely, specific irradiation dose is regulated and controled according to the thickness of cable；The heat of insulating layer and restrictive coating extends control 40 ~ 70%.
The hardness of the crosslinking TPE material is 80A, and soft, elasticity is good.
The crosslinking TPE material has the advantages that TPE and XLPE(crosslinked polyethylene), it can be improved the stabilization of cable operation
Property and anti-cracking performance, and it is able to satisfy 125 DEG C and 150 DEG C of use temperature.
The present invention is crosslinked the insulating layer and restrictive coating that TPE material is used for cable, therefore cable can be made to have excellent anti-tensile
Intensity, elongation at break, tearing strength.By being cross-linked to form reticular structure between material molecule, long-time service is not in cracking,
Compared to having high-flexibility and elastomeric advantage for XLPE material, conducive to the cable laying requirement of small-bend radius.
To sum up, the present invention overcomes cable existing problem of Cracking in long-term use, and guarantee the Gao Rou that cable uses
It is soft, while guaranteeing that cable can satisfy 1.5kv or higher voltage rating, have both general T PE insulated cable and XLPE insulation
The performance advantage of cable.
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 (5)
1. a kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible, for the insulating layer or/and shield of the cable to be made
Jacket layer；It is characterized by:
The raw material of the crosslinking TPE material comprises the following components in parts by weight:
25 ~ 35 parts of SEBS；
20 ~ 30 parts of polypropylene；
20 ~ 30 parts of phosphorus-nitrogen containing flame retardant；
5 ~ 10 parts of nano silica；
5 ~ 15 parts of naphthenic oil；
5 ~ 10 parts of crosslinking agent；
2 ~ 5 parts of lubricant；
2 ~ 3 parts of Masterbatch；
0.2 ~ 1 part of antioxidant；
The preparation process of the crosslinking TPE material is as follows:
Firstly, SEBS and naphthenic oil are stirred in low-speed mixer, mixing time is 2 ~ 4min, makes the abundant oil suction of SEBS
Swelling；
Then, polypropylene is added, continues to stir 2min, nano silica, fire retardant, lubricant, crosslinking agent, color is then added
Masterbatch, antioxidant, and 5 ~ 10min is stirred in high-speed mixer, obtain the homogeneous mixture of the crosslinking TPE material；
Finally, melt blending, processing temperature are 180 ~ 210 DEG C in double screw extruder by the mixture, material strip is squeezed out, with
Stretching and granulation afterwards；
Preliminary drying dry-cure is carried out to the crosslinking TPE material when cable squeezes out, drying temperature is 80 ~ 100 DEG C, drying time for 4 ~
The temperature of 6h, extrusion are controlled at 180 ~ 200 DEG C；
Cable is irradiated after the completion of squeezing out, and the irradiation dose of material is 12 ~ 17Mard/mm, and the heat of insulating layer and restrictive coating is prolonged
Control is stretched 40 ~ 70%.
2. crosslinking TPE material according to claim 1, it is characterised in that: the polyacrylic melt index is 0.8 ~ 2g/
10min。
3. crosslinking TPE material according to claim 1, it is characterised in that: the flash-point of the naphthenic oil be greater than 170 DEG C, and
Saturated hydrocarbon content therein is 89.2 ~ 94.0%.
4. crosslinking TPE material according to claim 1, it is characterised in that: the phosphorus-nitrogen containing flame retardant is using polyhydroxylated
Object composition is closed, the polyol includes following one or more of ingredients:
Pentaerythrite, ammonium polyphosphate, melamine.
5. crosslinking TPE material according to claim 1, it is characterised in that: the crosslinking agent uses TAIC, described in preparation
Before being crosslinked TPE material, TAIC first passes through coupling agent and is surface-treated；
The coupling agent is aminopropyl triethoxysilane, and parts by weight used are the 5 ~ 10% of the crosslinking agent；
The method of the surface treatment be the crosslinking agent is stirred in high-speed mixer with the coupling agent mix 2 ~
5min, until material is in uniformed powder shape and without particle；It is passed through 110 ~ 120 DEG C of hot-air after the completion of mixing and dries 3 ~ 5min,
It is cooled to 20 ~ 35 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811301490.3A CN109575499A (en) | 2018-11-02 | 2018-11-02 | A kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811301490.3A CN109575499A (en) | 2018-11-02 | 2018-11-02 | A kind of crosslinking TPE material of the high-elastic resistance to voltage cable of automobile-used highly-flexible |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017286A (en) * | 2014-05-28 | 2014-09-03 | 陕西泽康实业有限公司 | Expansive type high-flame-retardancy thermal-insulation polystyrene foam molding body and manufacturing method thereof |
| CN105038087A (en) * | 2015-08-19 | 2015-11-11 | 深圳市沃尔核材股份有限公司 | Halogen-free flame retardant high-tear-resistance wire and cable compound for electric vehicles and wire and cable production method |
| CN106380869A (en) * | 2016-08-29 | 2017-02-08 | 上海至正道化高分子材料股份有限公司 | 125-degree irradiation-crosslinked elastomer cable material used for new energy automobile high-voltage cable and manufacture method of elastomer cable material |
-
2018
- 2018-11-02 CN CN201811301490.3A patent/CN109575499A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017286A (en) * | 2014-05-28 | 2014-09-03 | 陕西泽康实业有限公司 | Expansive type high-flame-retardancy thermal-insulation polystyrene foam molding body and manufacturing method thereof |
| CN105038087A (en) * | 2015-08-19 | 2015-11-11 | 深圳市沃尔核材股份有限公司 | Halogen-free flame retardant high-tear-resistance wire and cable compound for electric vehicles and wire and cable production method |
| CN106380869A (en) * | 2016-08-29 | 2017-02-08 | 上海至正道化高分子材料股份有限公司 | 125-degree irradiation-crosslinked elastomer cable material used for new energy automobile high-voltage cable and manufacture method of elastomer cable material |
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Application publication date: 20190405 |