CN105061975B - A kind of heat discoloration charging wire material and its preparation method and application - Google Patents
A kind of heat discoloration charging wire material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of heat discoloration charging wire material and its preparation method and application, the material is mainly prepared by weight by following raw material:15~20 parts of 18~28 parts of SEBS, 10~20 parts of polypropylene, 5~15 parts of polyolefin elastomer, 10~20 parts of naphthenic oil, 1.5~3 parts of heat discoloration powder, 25~30 parts of magnesium hydroxide and bromide fire retardant.The present invention utilizes the triangular synergistic effect of SEBS, PP and POE by adding heat discoloration powder, and Mg (OH)2Synergistic effect between bromide fire retardant prepare can temperature sensor change and people can be allowed directly to observe its change and have the heat discoloration charging wire material of good mechanical properties and fire resistance concurrently.
Description
Technical field
The invention belongs to electric wire field, is related to a kind of charging wire material and its preparation method and application, more particularly to
A kind of heat discoloration charging wire material and its preparation method and application.
Background technology
Nearly 30 years, world economy high speed development, while make it that the environmental protection problem of facing mankind is increasingly serious.Industry
Tail gas with motor vehicle emission is that the world is multinational for this important factor for currently causing greenhouse effects, welding and influence life
Conferring and finding the method for reducing exhaust emissions and energy consumption.Development and living standards of the people with auto industry
Improve, the people are more and more with using to the demand of automobile, and the tail gas of motor vehicle emission also rapidly increases.Research and development Novel ring
Protecting energy-saving automobile becomes actualite, wherein the electric automobile that taps a new source of energy becomes first choice.Therefore novel electric vehicle fills
The exploitation of electric wire becomes line cable industry urgent problem.
Automobile charge cable often has two kinds of use patterns:One kind is to store on automobile, following automobile in different environments
Use;Another kind be placed in highway, garage, hotel, market, parking lot charging column on by long-time service.No matter that
Use pattern, cable are likely to be subject to include a variety of adverse environments such as daylight, weathering, humidity, seawater, greasy dirt, acid rain, frost
Influence, while also often to bend, draw in use, the mechanical damage such as inevitably to rub, scrape, crushing occur.
Now, charging electric motor vehicles electric wire material mostly selects PVC base as its electric wire sheath material, although this
Kind of charging wire insulation is good, surface abrasion resistance and price is relatively low, but since its burning can discharge the hydrogen chloride gas of severe toxicity,
With larger fire hazard, for there is very big potential threat in this during many automobile user uses.It is most of
Metal hydroxide combustion inhibitor is used in electric wire in order to reach flame retardant effect more, such as aluminium hydroxide and magnesium hydroxide, but by
In needing the dosage for being added up to 40~60wt% to can be only achieved flame-retardancy requirements, the Physical Mechanical of material can be often influenced again
Energy.Patent CN 102140192A disclose a kind of low-smoke halogen-free polyolefine composite and preparation method thereof, using Mg (OH)2
Polymer is carried out fire-retardant, its flame retarding efficiency is low, it is necessary to adding more than 60wt% can be only achieved higher flame-retardancy requirements, drops significantly
The low mechanical property of material.Patent CN 103073776A disclose a kind of halogen-free expanded flame-retardant wire cable insulating material combination
Thing, the raw material of the composition include following mass percent formula composition:Polyolefin 60~80%, halogen-free expansion fire retardant
15~35%, synergist 2~10%, compatilizer 1~10%, lubricant 0.1~1% and antioxidant 0.1~1%;Its is fire-retardant
Although the dosage of agent only accounts for the 15~35% of raw material weight, there is good fire resistance, the mechanical performance of material is not
It is preferable.
In electric automobile charging process, have larger current and be quickly filled with cable, make cable in use drastically
Heating;Meanwhile there is also the phenomenon that alternating bending is pullled in charging process, electric wire line body temperature easily caused by short circuit it is excessive and
Do not warn, there is the hidden danger of scald user.
For this reason, develop one kind can temperature sensor change and people can be allowed directly to observe its change and had concurrently good
The electric wire of mechanical performance, application prospect is very huge in electric system.
The content of the invention
For above-mentioned charge cable of the prior art in use because temperature is excessive without peace existing for warning
Full potential problem, and the problem of cable can not have good flame-retardance and good mechanical properties concurrently, the present invention provides one kind to feel
Temperature discoloration charging wire material and its preparation method and application, the present invention utilizes hydrogenation (benzene second by adding heat discoloration powder
Alkene-butadiene-styrene) block copolymer (SEBS), polypropylene (PP) and the triangular collaboration work of polyolefin elastomer (POE)
With, and Mg (OH)2Synergistic effect between bromide fire retardant prepare can temperature sensor change and make people direct
Observe its change and have good mechanical properties and the heat discoloration charging wire material of fire resistance concurrently.
For this purpose, the present invention uses following technical scheme:
In a first aspect, the present invention provides a kind of heat discoloration charging wire material, the material is mainly pressed by following raw material
Parts by weight meter is prepared:
Wherein, the parts by weight of SEBS can be 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27
Part or 28 parts etc.;The parts by weight of PP can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or
20 parts etc.;The parts by weight of POE can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.;Ring
The parts by weight of alkane oil can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts etc.;Sense
The parts by weight of warm color-change powder can be 1.5 parts, 1.7 parts, 2 parts, 2.3 parts, 2.5 parts, 2.7 parts or 3 parts etc.;The parts by weight of magnesium hydroxide
It can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts etc.;The parts by weight of bromide fire retardant can be 15 parts, 16 parts, 17 parts, 18
Part, 19 parts or 20 parts etc..
Preferably, the material is mainly prepared by weight by following raw material:
Into being preferably once that the material mainly has following raw material to be prepared by weight:
Wherein, hydrogenation (s-B-S) block copolymer (SEBS), polypropylene (PP) and the polyene
The triangular synergistic effect of olefin elastomer (POE) makes material have good mechanical performance.
The naphthenic oil is the petroleum distillate using cycloalkane as main component, its acid number<0.15mgKOH/g, pour point for-
40~-12 DEG C, saturated hydrocarbon content is 87.55%~93.86%, and arene content is 6.14%~11.96%, and asphalt content is
0~0.49%.
" the heat discoloration powder " is a kind of reversible temperature-sensitive electrochromic substance of microencapsulation, also known as warm variable pigments or temperature-sensitive
Powder, encapsulation stealth material, color forming agent and temperature control agent, select, are can be made into not by different temperature control factor materials
The colorant of the discoloration in synthermal section.This temperature-sensitive microcapsule powder particle diameter is 3~10 microns, and particle is spherical, and inside is to become
Color substance, outside are that about 0.2~0.5 micron of a thickness can neither dissolve the transparent outer cover that will not melt, can be with the upper of temperature
Rise, decline generation reversible color, show different colors at different temperature.
The Mg (OH)2Bromide fire retardant synergistic effect can be not only played, makes material that there is good fire resistance, together
When Mg (OH)2Antacid is alternatively arranged as, electric wire is suppressed the discoloration of copper conductor when being used under hygrothermal environment, while ensure that sense
Sensitiveness of the warm color-change powder to temperature.
In the present invention, the preparing raw material of the material is further included in smoke suppressant, antioxidant, lubricant or synergist arbitrarily
It is a kind of or at least two combination, it is described combination typical case but non-limiting examples have:The combination of smoke suppressant and antioxidant, antioxygen
The combination of the combination of agent and lubricant, lubricant and synergist.
It is described above to further include any one in smoke suppressant, antioxidant, lubricant or synergist or at least two
Combination, refers to may be selected not add during heat discoloration charging wire material is prepared according to needs of production, also can root
According to the combination for needing any one in addition smoke suppressant, antioxidant, lubricant or synergist or at least two.
In the present invention, the smoke suppressant is for any one in zinc borate, ammonium octamolybdate, molybdenum dioxide or tin oxide or at least
Two kinds of combination, the combination is typical but non-limiting examples have:The combination of zinc borate and ammonium octamolybdate, ammonium octamolybdate and dioxy
Change the combination of molybdenum, the combination of molybdenum dioxide and tin oxide, the combination of zinc borate, ammonium octamolybdate and molybdenum dioxide, zinc borate, eight molybdenums
Combination in sour ammonium, molybdenum dioxide and tin oxide.
Preferably, the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant CA, antioxidant
2246th, any one in antioxidant 3114 or antioxidant 3125 or at least two combination, the combination are typical but non-limiting
Example has:The combination of the combination of antioxidant 1010 and antioxidant 1076, antioxidant 264 and antioxidant CA, antioxidant 2246 and anti-
The combination of oxygen agent 3114, the combination of antioxidant 1010, antioxidant 1076 and antioxidant 264 etc..
Preferably, the lubricant is any one in erucyl amide, oleamide or stearic amide or at least two
Combination, it is described combination typical case but non-limiting examples have:The combination of erucyl amide and oleamide, oleamide and stearic acid
The combination of acid amides, the combination of erucyl amide, oleamide and stearic amide etc..
Preferably, the synergist is to appoint in silica, carborundum, zirconium oxide, zinc oxide, titanium dioxide or aluminium oxide
Anticipate a kind of or at least two combinations, the combination typical case but non-limiting example has:The combination of silica and carborundum, carbonization
The combination of silicon, zirconium oxide and zinc oxide, the combination etc. of zirconium oxide, zinc oxide, titanium dioxide and aluminium oxide.
In the present invention, the preparing raw material of the material does not include surface conditioning agent and/or curing agent, i.e., the system of described material
Standby raw material does not include surface conditioning agent, and the preparing raw material of the material does not include curing agent, and the preparing raw material of the material is not wrapped
Include surface conditioning agent and curing agent;The surface conditioning agent and curing agent are the conventional addition in electric wire and cable material production process
Agent, also refers to the additive for improving interface performance in electric wire and cable material production process and plays the additive of solidification.
Specific surface conditioning agent is not such as silane coupling agent, titanate coupling agent, aluminate coupling agent or methyl hydrogen silicon, but not
It is limited to these these cited materials;Specific curing agent such as vinyl triamine, diaminocyclohexane, di-2-ethylhexylphosphine oxide hexamethylene
Amine, diethyl amino propylamine, m-xylene diamine or diaminodiphenyl-methane etc., but it is not limited to these these cited materials.
It is due in preparation process not add surface conditioning agent and curing agent in the present invention, and material internal produces sometimes
Powerful shrinkage stress, if addition surface conditioning agent and curing agent, not only have impact on the mechanical performance of material, also results in temperature-sensitive change
Toner microcapsule shell ruptures, and other chemical substances, which enter inside pigment, makes it lose discoloration.
In the present invention, the bromide fire retardant is deca-BDE, tetrabromobisphenol A, decabromodiphenylethane, eight bromo ether or bromine
Change any one in polystyrene or at least two combination, the combination is typical but non-limiting example has:Deca-BDE and
The combination of the combination of the combination of tetrabromobisphenol A, decabromodiphenylethane and eight bromo ether, eight bromo ether and brominated Polystyrene, ten bromines two
The combination of phenylate, tetrabromobisphenol A and decabromodiphenylethane, deca-BDE, tetrabromobisphenol A, decabromodiphenylethane, eight bromo ether and
Combination of brominated Polystyrene etc..
In the present invention, the material includes at least two color changes, for example, two kinds of color changes, three kinds of color changes,
Four kinds of color changes or more kind.
Preferably, the material includes the color change of at least two different temperatures induction ranges.
The material has the color change of various temperature grade, such as can have corresponding color from -40 DEG C~150 DEG C
Change.By needing to select the material for adding different heat discoloration powder, when the temperature that the cable is perceived is in predetermined temperature
Color is constant when within such as 40 DEG C of scope, and when the temperature that the cable is perceived is more than 40 DEG C, the material is become by black
For red;For another example when the temperature that the cable is perceived is more than 60 DEG C, the material is changed into yellow from red.Above color
Change procedure is reversible process, after the temperature that the cable is perceived is reverted within predetermined temperature range, the material
Color also revert to the color before changing, i.e., described material includes at least two color changes, and at least two different temperatures
The color change of induction range.
Can show that predetermined color by cable at a predetermined temperature, can easily visual test cable temperature
State;And the state of temperature of cable can be determined on whole cable.The temperature that the cable is perceived be by cable in itself
The temperature rise produced is loaded, or the temperature that cable is put variation of ambient temperature and produced changes.
Second aspect, the present invention provides the preparation method of above-mentioned heat discoloration charging wire material, the preparation method is:
All raw materials in addition to heat discoloration powder are sequentially added in mixer by formula ratio and are mixed, are uniformly mixed
Heat discoloration powder is added afterwards to continue to mix, and the good material of mixture is transferred in double screw extruder and carries out extruding pelletization.
Preferably, the processing temperature of the double screw extruder be 150~200 DEG C, such as 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 190 DEG C or 200 DEG C etc., elect 180~190 DEG C as.
The third aspect, the present invention provides the charging electric wire that above-mentioned heat discoloration charging wire material is prepared.
Fourth aspect, the present invention provides the application of above-mentioned heat discoloration charging wire material, it leads applied to electric automobile
Domain.
Compared with prior art, the invention has the advantages that:
(1) electric wire being prepared using heat discoloration of the present invention charging wire material is placed in unfavorable mounting ring
When causing cable in an overheated state under border and overcurrent condition, material can respond predetermined heat resisting temperature scope and change
It is predetermined color so as to play the role of warning, excludes security risk.
(2) hydrogenation (s-B-S) block copolymer (SEBS), polypropylene (PP) and polyolefin are utilized
Elastomer (POE) triangular synergistic effect, and Mg (OH)2Synergistic effect between bromide fire retardant, which is prepared, to be felt
Answer temperature change and people can be allowed directly to observe its change and have good mechanical properties and the heat discoloration of fire resistance concurrently
Charge wire material, application heat discoloration charging wire material is tested for the property to obtain, its tensile strength reaches more than 20MPa, breaks
Split elongation and reach 600%, flame retardant rating is V-0 grades.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
The performance test methods of each embodiment are as follows in the present invention:
Mechanical property is carried out using ASTM D638-89 standards at 23 DEG C, rate of extension 500mm/min;Fire resistance
Test uses U.S. UL94 vertical burn test standards;Heat aging performance uses GB/T2951.2 testing standards, and aging condition is
Aging 168h at 136 ± 2 DEG C.
Embodiment 1:
By 23 parts of SEBS, 15 parts of PP, 10 parts of POE, 15 parts of naphthenic oils, 26 parts of Mg (OH)2With 16 parts of deca-BDEs successively
Add in mixer and mixed, add 2.3 parts of orange heat discoloration powder after mixing and continue to mix, by the good material of mixture
It is transferred in double screw extruder and carries out extruding pelletization in 185 DEG C, obtains heat discoloration charging wire material.
Resulting materials are in orange at 45 DEG C, it is in yellow after surrounding environment or itself temperature are more than 45 DEG C.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Embodiment 2:
By 20 parts of SEBS, 13 parts of PP, 7 parts of POE, 13 parts of naphthenic oils, 25 parts of Mg (OH)2, 15 parts of tetrabromobisphenol As, 5 parts of suppression cigarettes
Agent zinc borate and 6 parts of antioxidant 1010s are sequentially added in mixer and mixed, and add 2 parts of dark red heat discolorations after mixing
Powder continues to mix, and the good material of mixture is transferred in double screw extruder and carries out extruding pelletization in 180 DEG C, obtains heat discoloration
Charge wire material.
Resulting materials are in black at 40 DEG C, it takes on a red color after surrounding environment or itself temperature are more than 40 DEG C.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Embodiment 3:
By 25 parts of SEBS, 17 parts of PP, 13 parts of POE, 17 parts of naphthenic oils, 27 parts of Mg (OH)2, 17 parts of decabromodiphenylethane, 6 parts
Smoke suppressant silica, 8 parts of lubricant erucyl amides and 6 parts of smoke suppressant ammonium octamolybdates are sequentially added in mixer and mixed,
After mixing add 2.5 parts of orange red temperature-sensitive toners continue to mix, by the good material of mixture be transferred in double screw extruder in
180 DEG C of progress extruding pelletizations, obtain heat discoloration charging wire material.
Resulting materials are in orange at 40 DEG C, it takes on a red color after surrounding environment or itself temperature are more than 40 DEG C.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Embodiment 4:
Except the parts by weight of SEBS are 18 parts, the parts by weight of PP are 10 parts, the parts by weight of POE are 5 parts, the weight of naphthenic oil
Part is 10 parts, the parts by weight of mixing heat discoloration powder are 1.5 parts, Mg (OH)2Parts by weight be 25 parts and bromide fire retardant eight
For 15 especially, the additive amount of other steps and other materials is in the same manner as in Example 1 for the parts by weight of bromo-ether.
Resulting materials are in black below 40 DEG C, are taken on a red color when surrounding environment or itself temperature are between 40~60 DEG C,
When surrounding environment or itself temperature more than 60 DEG C are in then yellow.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Embodiment 5:
Except the parts by weight of SEBS are 28 parts, the parts by weight of PP are 20 parts, the parts by weight of POE are 15 parts, the weight of naphthenic oil
Amount part is 20 parts, the parts by weight of heat discoloration powder are 3 parts, Mg (OH)2Parts by weight be 30 parts and bromide fire retardant eight bromo ether
Parts by weight for 20 especially, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Comparative example 1:
In addition to not adding SEBS, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Comparative example 2:
In addition to not adding PP, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Comparative example 3:
In addition to not adding POE, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Comparative example 4:
Except not adding Mg (OH)2Outside, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Comparative example 5:
In addition to not adding bromide fire retardant, the additive amount of other steps and other materials is in the same manner as in Example 1.
Mechanics Performance Testing is carried out to resulting materials and vertical burn test, test result are listed in Table 1 below.
Table 1:Embodiment 1-5 and comparative example 1-5 resulting materials performance test tables
The result of integrated embodiment 1-5 and comparative example 1-5 can be seen that the present invention using hydrogenation (styrene-butadiene-
Styrene) block copolymer (SEBS), polypropylene (PP) and polyolefin elastomer (POE) triangular synergistic effect, and Mg
(OH)2Synergistic effect between bromide fire retardant prepare can temperature sensor change and people can be allowed directly to observe it
Change and have good mechanical properties concurrently and the heat discoloration of fire resistance charging wire material, to application heat discoloration charging wire material
It is tested for the property to obtain, its tensile strength reaches more than 20MPa, and elongation at break reaches 600%, and flame retardant rating is V-0 grades.Together
When, the electric wire being prepared using heat discoloration of the present invention charging wire material is placed in unfavorable installation environment and mistake
When causing cable in an overheated state under current status, material can respond predetermined heat resisting temperature scope and change into predetermined
Color excludes security risk so as to play the role of warning.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within protection domain and the open scope.
Claims (16)
- The wire material 1. a kind of heat discoloration charges, it is characterised in that the material is mainly prepared by weight by following raw material Obtain:The preparing raw material of the material does not include surface conditioning agent and/or curing agent.
- 2. material according to claim 1, it is characterised in that the material is mainly prepared by weight by following raw material Obtain:
- 3. material according to claim 2, it is characterised in that the material mainly has following raw material to prepare by weight Obtain:
- 4. material according to claim 1, it is characterised in that the preparing raw material of the material further includes smoke suppressant, antioxygen Any one in agent, lubricant or synergist or at least two combination.
- 5. material according to claim 4, it is characterised in that the smoke suppressant is zinc borate, ammonium octamolybdate, molybdenum dioxide Or any one in tin oxide or at least two combination.
- 6. material according to claim 4, it is characterised in that the antioxidant for antioxidant 1010, antioxidant 1076, Any one in antioxidant 264, antioxidant CA, antioxidant 2246, antioxidant 3114 or antioxidant 3125 or at least two group Close.
- 7. material according to claim 4, it is characterised in that the lubricant is erucyl amide, oleamide or tristearin Any one in sour acid amides or at least two combination.
- 8. material according to claim 4, it is characterised in that the synergist for silica, carborundum, zirconium oxide, Any one in zinc oxide, titanium dioxide or aluminium oxide or at least two combination.
- 9. material according to claim 1, it is characterised in that the bromide fire retardant is deca-BDE, tetrabromobisphenol A, any one in decabromodiphenylethane, eight bromo ether or brominated Polystyrene or at least two combination.
- 10. material according to claim 1, it is characterised in that the material includes at least two color changes.
- 11. material according to claim 10, it is characterised in that the material includes at least two different temperatures sensing model The color change enclosed.
- 12. according to the preparation method of any one of the claim 1-11 materials, it is characterised in that the preparation method of the material For:All raw materials in addition to heat discoloration powder are sequentially added in mixer by formula ratio and are mixed, are added after mixing Enter heat discoloration powder to continue to mix, the good material of mixture is transferred in double screw extruder and carries out extruding pelletization.
- 13. preparation method according to claim 12, it is characterised in that the processing temperature of the double screw extruder is 150~200 DEG C.
- 14. preparation method according to claim 13, it is characterised in that the processing temperature of the double screw extruder is 180~190 DEG C.
- A kind of 15. charging electric wire being prepared using any one of the claim 1-11 materials.
- 16. according to the application of any one of the claim 1-11 materials, it is applied to electric automobile field.
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