CN103965575A - Charging wire material for electric vehicles and preparation method thereof - Google Patents
Charging wire material for electric vehicles and preparation method thereof Download PDFInfo
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- CN103965575A CN103965575A CN201410204579.3A CN201410204579A CN103965575A CN 103965575 A CN103965575 A CN 103965575A CN 201410204579 A CN201410204579 A CN 201410204579A CN 103965575 A CN103965575 A CN 103965575A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention discloses a charging wire material for electric vehicles and a preparation method thereof. The charging wire material is prepared by the following steps: adding a plastic elastic soft material and white oil to a high-speed mixer and stirring so that the white oil is completely and uniformly absorbed; sequentially adding an activated halogen-free composite flame retardant, 0-20 parts of a charcoal forming agent, a smoke suppressor, an oxidant, a lubricant, a wear-resistant agent, a coupling agent and a bulking agent to the high-speed mixer and mixing; transferring mixed materials to a reactant twin-screw extruder hopper, and implementing melt-blending, extrusion and granulation at processing temperature of 150-250 DEG C to obtain a product. The fire-resistant wire composite material prepared by the invention has the advantages of being halogen-free, low in smoke, soft and easy to curl, wear resistant on surface, easy to process and form, and recyclable; the composite material can better meet using requirements of charging wire material for current electric vehicles.
Description
Technical field
The present invention relates to a kind of charging electric motor vehicles electric wire material and preparation method thereof.
Background technology
Nearly 30 years, world economy high speed development made the environmental protection problem of facing mankind increasingly serious simultaneously.At Global Auto industrial circle, the pollution causing due to vehicle exhaust causes people's extensive concern, the R&D and promotion of new-energy automobile is obtained to many countries to be paid attention to, automobile vendor of many developed countries releases the electromobile of different brands successively, builds vehicle charging station to meet the needs of growing electric automobile market home in scope simultaneously.And at present, charging electric motor vehicles electric wire material mostly still selects Halogen PVC base material as its electric wire sheath material, although this kind of charging electric wire good insulating, surface abrasion resistance and price are relatively low, but because its burning can discharge hypertoxic hydrogen chloride gas, have larger disaster hidden-trouble, this is for there being very large potential threat in many electromobile users use procedure.At present, although also there are many other materials to be developed for charging electric vehicle electric wire material, for example comprise that polyolefine cross-linked material, vulcanized rubber material, elastomer material etc. constantly release, but do not reach all the time it completely and damage, be easy to for halide-free smokeless, soft easily curling, surface abrasion resistance the requirement of machine-shaping, recoverable etc.
Summary of the invention
The object of the present invention is to provide a kind of halide-free smokeless, soft easily curling, surface abrasion resistance to damage, be easy to charging electric motor vehicles electric wire material of machine-shaping, recoverable and preparation method thereof.
Technical solution of the present invention is:
A kind of charging electric motor vehicles electric wire material, is characterized in that: the raw material by weight components is made:
100 parts of plasticity-elasticity soft materials
Plasticity-elasticity soft material of the present invention is Powdered hydrogenation (Ben Yi Xi ?Ding bis-Xi ?vinylbenzene) segmented copolymer (SEBS), its molecular weight is 8～280,000, the ratio of phenylethylene/butadiene be 2:8 to 4:6, density is 0.85～0.95.Preferred SEBS molecular weight is 10～250,000.
The technical grade paraffin oil of white oil of the present invention for obtaining in petroleum cracking process, flash-point is 200～250 DEG C, and kinematic viscosity is 30～150cSt at 40 DEG C, and density is 0.8～0.9.Preferred white oil flash-point is 200～230 DEG C, and kinematic viscosity (40 DEG C) is 40～80cSt.
Polyolefine material of the present invention be polyethylene (PE), polypropylene (PP), Yi Xi ?octene random copolymers (POE), Yi Xi ?random copolymer of propylene (POP) wherein a kind of, or any mixture of above several materials; Its melting index is 2～30g/10min (230 DEG C, 2.16kg), and mooney viscosity ML1+4 (121 DEG C) is 3～45.
Halogenless composite fire retardant of the present invention is the mixture of the on-liquid class phosphonium flame retardants such as inorganic combustion inhibitor and ammonium polyphosphate (APP), melamine salt, polyphosphonitrile or phosphoric acid ester such as super fine magnesium hydroxide (MDH), aluminium hydroxide (ATH), hydrated magnesium silicate or the potter's clay of organic modification of surface.Preferred inorganic combustion inhibitor is surperficial through organically-modified, the magnesium hydroxide of grain size≤3 μ m.Preferred phosphonium flame retardant is phenoxy group polyphosphonitrile, its heat decomposition temperature >=300 DEG C, and molecular structure can adopt following general structure to represent:
Wherein, n is the polymerization degree, is the positive integer between 3～30.
Char-forming agent of the present invention is the one of polycarbonate (PC), polyhenylene ether (PPO), epoxy resin or resol.Preferred char-forming agent is the polyhenylene ether of intrinsic viscosity 0.3～0.5cm3/g, and its molecular weight is 2～60,000, and second-order transition temperature >=210 DEG C can adopt following structural formula to represent:
Wherein, be the positive integer between 150～500.
Smoke suppressant of the present invention is the one of zinc borate, ammonium octamolybdate, molybdenum dioxide, stannic oxide, and preferred smoke suppressant is ammonium octamolybdate.
Composite antioxidant of the present invention is the binary mixture of antioxidant 1010 and irgasfos 168, anti-oxidant DLTP or oxidation inhibitor DSTP.
Lubricant of the present invention is erucicamide, amine hydroxybenzene or stearic amide, and this amides lubricant can also use as dispersion agent simultaneously.
Anti-wear agent of the present invention is the nano silicon of surface organic modification.
Coupling agent of the present invention is silane coupling agent, specifically can select amino silicane coupling agent or vinyl silicane coupling agent.
Expanding material of the present invention be Yi Xi ?vinyl acetate copolymer (EVA), maleic anhydride graft polyethylene, maleic anhydride graft polypropylene, maleic anhydride graft Yi Xi ?octene copolymer, maleic anhydride graft Yi Xi ?hydrogenation (Ben Yi Xi ?Ding bis-Xi ?the vinylbenzene) segmented copolymer of propylene copolymer or maleic anhydride graft.Above-mentioned preferred expanding material is that percentage of grafting is 1.2～1.5% maleic anhydride graft hydrogenation (Ben Yi Xi ?Ding bis-Xi ?vinylbenzene) segmented copolymer.
Preparation method is as follows, below material addition all represent with parts by weight:
The plasticity-elasticity soft material of 100 parts and 50～300 parts of white oils are added in high-speed mixer, high-speed stirring makes white oil by full and uniform absorption, then by the polyolefine material of 50～200 parts, 50～200 parts of Halogenless composite fire retardants, the char-forming agent of 0～20 part, the smoke suppressant of 0～3 part, the oxidation inhibitor of 0.5～1.0 part, the lubricant of 0.3～3.0 part, the anti-wear agent of 2～8 parts, the coupling agent of 0～2.0 part, the expanding material of 0～5 part adds in high-speed mixer successively, utilize high speed rotating and the frictional heat of mixing machine, make various materials therebetween reach even mixing and dispersion.Mixed material is transferred to the hopper of reactive twin screw extruder by high mixer, melt blending extruding pelletization under the processing temperature of 150～250 DEG C, obtains the eco-friendly matrix material that can be used for charging electric vehicle electric wire.This kind of advanced composite material is easy to machine-shaping, extruded velocity is fast, mold temperature is low, recoverable, is the new selection that substitutes PVC base charging electric vehicle electric wire.
One of main raw material(s) of the present invention hydrogenation (Ben Yi Xi ?Ding bis-Xi ?vinylbenzene) segmented copolymer (SEBS) suitability for industrialized production introducing to the market, comprise the companies such as section of the U.S. rises, Japanese Kuraray, Taiwan rubber, Sinopec, its all trade mark rosin productss all have sale in Chinese market, material range of choice is large, and price is relatively moderate.And another main raw material(s) technical grade paraffin oil adopting in the present invention, for petroleum cracking process gained, petrochemical complex relevant enterprise all has production marketing at home, and cheap, itself and rubber mix not only can be used as plasticising lubricant and use, and have also reduced material total cost simultaneously.In the present invention, adopt high-speed mixer, white oil is fully mixed and is absorbed with rubber, both ratios can regulate according to the final hardness of designed material, increase the oil-filled amount of rubber and can lower material hardness, the larger hardness of oil-filled ratio is lower, otherwise hardness is higher, its regulation range is very broad.In the present invention, anti-wear agent nano silicon is pre-dispersed in white oil, thereby effectively avoid because the specific surface energy of nanometer grade silica is compared with the reunion causing greatly and be difficult for the difficulty of disperseing, simultaneously also corresponding phenomenons such as the excessive flow difficulties causing of course of processing melt viscosity of having avoided.
The Halogenless composite fire retardant adopting in the present invention is polyphosphonitrile and super fine magnesium hydroxide mixture, and dispersiveness, through organic modification, has been improved in magnesium hydroxide surface; Phosphonium flame retardant adopts phenoxy group polyphosphonitrile.Preferred char-forming agent is polyphenylene oxide resin (PPO), by regulating the adding proportion of fire retardant, char-forming agent, gives full play to each component synergy, makes it reach the object of highly effective flame-retardant.
The preparation method who adopts in the present invention is that single stage method melt extrudes, the simple easily operation of whole production process, and processing temperature is lower, and actual temperature is lower than 210 DEG C, energy efficient.The forcing machine that preparation process adopts be Shuan Luo Gan ?single screw rod two steps type forcing machine, the screw rod module of twin screw extruder adopts the fit system of " Mi Lian ?Jian Qie ?banburying " to carry out alternate combinations, preferred screw slenderness ratio is >=52.All raw material, after high-speed mixer mixes, by shearing and the banburying dual function of twin screw, reaches molecular level blend and merges object, then pass through the conveying of single screw rod, finally carries out air-cooled rear pelletizing, the flame-proof composite material that obtains preparing.Whole production process is for once completing, and material, without tank refrigerating work procedure, can directly be packed warehouse-in without dry after pelletizing.
The fire-resistant wire material subsequent machining technology of preparing in the present invention is simple and convenient, without complicated links such as crosslinked and sulfurations, completely can machine-shaping on conventional P VC base electric wire forcing machine, and avoid the reinvestment of equipment, save cost; And after materials'use, easily reclaim and again utilize, also save the energy.Because this material flowability is good, extruded velocity is fast, can reach 100 meters/more than min extrusion and become linear velocity when wall thickness 0.5～2.0mm, has higher production efficiency.
The electric wire material halide-free smokeless of preparing in the present invention, extrusion become after line flame retardant test can reach VW ?1 grade.The charging electric wire particularly soft of preparation, is easily curled into dish, and this is conducive to terminal user carries out curling laying in electromobile inside after finishing using.Meanwhile, its surface abrasion resistance can be excellent, effectively avoided its use procedure because pull the damage that friction causes.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
The present invention will be described in more details technical scheme of the present invention by the following specific embodiments, but the present invention is not limited to specific embodiment proposed below.
In the present invention, the information such as the trade mark, physical index of following examples and comparative example main raw material(s) used is listed in table 1:
Table 1
| Material | The material information describing in detail |
| SEBS‐Ⅰ | Ke Teng company: trade mark G1654, S/B=31/69, molecular weight 180,000 |
| SEBS‐Ⅱ | Ke Teng company: trade mark G1650, S/B=30/70, molecular weight 110,000 |
| Paraffin oil | The two dragons of Korea S: trade mark N250, viscosity 45cSt, 220 DEG C of flash-points |
| PP | Korea S SK: trade mark R370Y, hardness 65D, the molten 18g/10min that refers to |
| POP‐Ⅰ | Mobil: the trade mark 3980, hardness 86A, intensity 19.8Mpa, the molten 8g/10min that refers to |
| POP‐Ⅱ | Mobil: the trade mark 6202, hardness 61A, intensity 9.5Mpa, the molten 20g/10min that refers to |
| TPU | Yantai ten thousand China: trade mark WHT ?1190, hardness 90A, intensity 37Mpa, stretches rate 440% |
| TPV | The U.S. all puts down on mountain: the trade mark 201 ?80, hardness 86A, intensity 11Mpa, stretches rate 420% |
| Polyphosphonitrile | The blue chemical industry that prints in Zibo: hexaphenoxycyclotriphosphazene, phosphorus content 14%, nitrogen content 8% |
| MDH‐Ⅰ | Albemarle Corporation of Germany: trade mark H7, particle diameter≤3 μ m |
| MDH‐Ⅱ | Albemarle Corporation of Germany: trade mark H7C/2, surface is through organic modification |
| Become Tan Ji ?I | ASAHI company of Japan: PPO, trade mark S201A, intrinsic viscosity 0.4cm3/g |
| Become Tan Ji ?II | Japan Supreme Being people: PC powder, trade mark L ?1250Y, density 1.2g/cm3 |
| Nanometer SiO2 | Goldschmidt chemical corporation: gas phase sio2, trade mark AEROSIL R202, silane-modified |
| Ammonium octamolybdate | MCA company of the U.S., median size size≤2 μ m, decomposition temperature >=280 DEG C |
| 1010 | Vapour Bagong department: CAS No:6683 ?19 ?8,110～125 DEG C of fusing points |
| DSTP | Taiwan Shuan Jian chemical company: 63～68 DEG C of fusing points |
| Erucicamide | The sky, Sichuan chemical company: CAS No:112 ?84 ?5,80 DEG C of fusing points |
| SEBS‐g‐MA | Ke Teng company: trade mark FG1901X, molten 7g/10min, the MA percentage of grafting 1.3% of referring to |
Composite material by adopting twin screw extruder preparation in the following stated embodiment and comparative example.Selection rate of feeding is 15Hz, engine speed 300rpm, and melt blending extruding pelletization under the processing temperature of 180～200 DEG C, obtains a kind of composite flame-proof material that can be used for charging electric vehicle electric wire.Finally utilize general PVC electric wire extrusion equipment to carry out extrusion and become line, set 190 DEG C of electric wire extruder temperatures, squeeze 80～100 meters/min of linear velocity, electric wire is outer by the about 0.5mm of wall thickness.
Specific embodiment 1～5 and corresponding comparative example formula composition are listed in respectively in table 2 and table 3:
Table 2
Table 3
Plasticity-elasticity soft material and white oil are added in high-speed mixer, high-speed stirring makes white oil by full and uniform absorption, then by polyolefine material, Halogenless composite fire retardant, char-forming agent, smoke suppressant, oxidation inhibitor, lubricant, anti-wear agent, coupling agent, expanding material add successively in high-speed mixer, utilize high speed rotating and the frictional heat of mixing machine, make various materials therebetween reach even mixing and dispersion.Mixed material is transferred to the hopper of reactive twin screw extruder by high mixer, melt blending extruding pelletization under the processing temperature of 150～250 DEG C, obtains the eco-friendly matrix material that can be used for charging electric vehicle electric wire.
A kind of charging electric motor vehicles electric wire material obtaining in above embodiment and comparative example, its Mechanics Performance Testing all adopt ASTM D638 ?89 standards at 23 DEG C, carry out, draw speed select 500mm/min; Flame retardant properties test adopts U.S. UL94 vertical combustion testing standard, and burning specimen in use is of a size of the elongate in shape of 125mm × 12.5mm × 6.0mm; Heat aging performance adopts GB/T2951.2 testing standard, and aging condition is the test result of aging 168 hours at 136 ± 2 DEG C.Above test condition is except flame retardant test, and this material extrusion becomes the test after line to be also suitable for.After extrusion, charge electric wire flame retardant test adopt UL1581,1080VW ?1 vertical combustion standard.The resistance to test condition of separating out of electric wire: 85 DEG C of constant humidity 85 of constant temperature, place 168 hours.Electric wire thermal shock test condition: electric wire is placed after 1 hour at 150 DEG C, is cooled to room temperature, observes electric wire surface and has or not cracking.Test that electric wire is wear-resistant: carry out according to wear-resisting test condition in electric wire UL1581.
The fundamental property test of the above-mentioned electric wire matrix material of the present invention adopts t1 to represent, aging resistance test adopts t2 to represent, the test of UL94 vertical combustion adopts t3 to represent.Concrete method for expressing: density (g/cm3) adopt t1 ?I represent, hardness (Shao Shi A) adopts t1 ?II to represent, melting index (g/10min) adopt t1 ?III represent, tensile strength (Mpa) adopt t1 ?IV represent, elongation at break (%) adopt t1 ?V represent; Strength retention (%) after aging adopt t2 ?I represent, the extension at break conservation rate (%) after aging adopt t2 ?II represent.
The above-mentioned extrusion charging electric wire Mechanics Performance Testing of the present invention adopts T1 to represent, wherein: tensile strength (Mpa) adopts T1 ?I to represent, elongation at break (%) adopts T1 ?II to represent; Aging resistance test adopts T2 to represent, wherein: the strength retention (%) after aging adopt T2 ?I represent, the extension at break conservation rate (%) after aging adopt T2 ?II represent; UL1581VW ?1 vertical combustion adopt T3 to represent, resistance toly separate out test and adopt T4 to represent, thermal shock test adopts T5 to represent, surface abrasion resistance damages test and adopts T6 to represent, the apparent and texture of electric wire adopts T7 to represent.
In the above embodiments 1～5 of the present invention, the test result of product and the requirement of performance index and reference standard are listed in table 4.
The above-mentioned comparative example C of the present invention ?1～C ?in 5 the test result of product and the requirement of performance index and reference standard be listed in table 5.
The above-mentioned comparative example C of the present invention ?6, E ?1～E ?in 4 the test result of product and the requirement of performance index and reference standard be listed in table 6.
Table 4
Table 5
Table 6
Embodiment 1: adopt the oil-filled SEBS of N250 white oil ?G1654, PP ?R370Y composition TPE ?S base material, adopting the compound system of hexaphenoxycyclotriphosphazene and organic modification MDH H7C/2 composition is fire retardant, above-mentioned two kinds of fire retardant ratios are 1:1, adopt Japanese Asahi Kasei Corporation PPO ?S201A be char-forming agent, adopting silane-modified nanometer SiO2 is anti-wear agent, and other each component refers in the embodiment 1 of table 2.Test result by embodiment in table 41 can be found: prepared flame-proof composite material and extrusion electric wire have good mechanical property and flame retardant properties, electric wire tensile strength 16.5Mpa, elongation at break 413%, UL94 vertical combustion test result V ?0 grade, UL1581 test result be VW ?1 grade.Electric wire is 92% through 136 DEG C of 168 hours aging stretching strength retentivities, and elongation at break conservation rate is 94%, all substantially exceeds the regulation (>=75%) of UL1581 thermal ageing standard; Without cracking phenomena, show excellent heat aging property through thermal shocking.The apparent light of electric wire is fine and smooth, soft, without separating out, without scratch, show fabulous over-all properties, can meet the requirement of current charging electric motor vehicles electric wire.
Embodiment 2: adopt SEBS ?G1650 replace SEBS ?G1654, through N250 white oil oil-filled with PP ?R370Y composition base material, other each component composition is equal to the composition of embodiment 1.Test result by embodiment in table 42 can be found: compare with embodiment 1, the flame-proof composite material of preparation and the tensile strength of extrusion electric wire, strength retention after aging all slightly reduce, but all still far away higher than the lower limit requirement of UL standard, except the melting index of material is increased to 8.6g/10min by 2.5g/10min, other physical property changes less generally.In general, electric wire and material all have excellent over-all properties, have met the requirement of charging electric motor vehicles electric wire.Meanwhile, compared with embodiment 1, in embodiment 2, material flowability increases, and extrudes and is more prone to for the electric wire thick compared with thin-walled.
Embodiment 3: adopt SEBS ?G1650 replace 50% addition SEBS ?G1654, through white oil N250 oil-filled with PP ?R370Y composition TPE ?S base material, other each component composition is equal to the composition of embodiment 1 and embodiment 2.Test result by embodiment in table 43 can be found: the performance of the flame-proof composite material of preparation and extrusion electric wire is between embodiment 1 and the physical property of embodiment 2, and over-all properties is good, meets the service requirements of charging electric motor vehicles electric wire completely.
Comparative example C ?1: on the basis of embodiment 3, keep hexaphenoxycyclotriphosphazene and MDH H7C/2 to add total amount, only change the adding proportion (changing 2:1 into by original 1:1) of two kinds of fire retardants, other each component and ratio all remain unchanged.By comparative example C in table 5 ?1 test result can find: the flame retardant properties of the flame-proof composite material of preparation and extrusion electric wire reduces, the test of UL94 vertical combustion be only V ?1 grade, UL1581 test be only FT ?2 grades, electric wire is fire-retardant can not be tested by vertical combustion.Therefore, its flame retardant properties does not reach the service requirements of charging electric motor vehicles electric wire.
Comparative example C ?2: on the basis of embodiment 3, keep hexaphenoxycyclotriphosphazene and MDH H7C/2 to add total amount, only change the adding proportion (changing 1:2 into by original 1:1) of two kinds of fire retardants, other each component and ratio all remain unchanged.By comparative example C in table 5 ?2 test results can find: the flame-proof composite material hardness of preparation slightly increases (being increased to 92A by 90A), the flame retardant properties of extrusion electric wire declines obviously, UL1581 test is Fail, and its flame retardant properties can not reach requirement completely.
Comparative example C ?3: on the basis of embodiment 3, only change the kind of char-forming agent: change char-forming agent PC into by original char-forming agent PPO, keep the composition of other each component and ratio all constant.In table 5 comparative example C ?3 test results: UL94 vertical combustion V ?2 grades, when burning, there is molten drop phenomenon, become charcoal reduce; Electric wire UL1581 test FT ?2 grades, flame retardant properties declines, and can not reach the fire-retardant requirement of charging electric motor vehicles electric wire.
Comparative example C ?4: on the basis of embodiment 3, only change the kind of base material, by equivalent polyester type TPU replace above-mentioned TPE ?S base material, keep composition and the ratio of the components such as fire retardant, char-forming agent all constant.Comparative example C ?4 test results in table 5: 2 grades of UL94 vertical combustion V ?, composite hardness is increased to 98A by 90A, and electric wire flexibility reduces greatly, and there is separating out phenomenon in fixed temperature and humidity test, and elongation at break is reduced to 232% by 455%.Poor-performing generally, does not reach the service requirements of charging electric motor vehicles electric wire.
Comparative example C ?5: on the basis of embodiment 3, only change the kind of part base material: TPU replaces oil-filled SEBS by equivalent polyester type, with PP ?R370Y composition base material, other each component is equal to the composition of embodiment 3.From comparative example C in table 5 ?5 test result: with comparative example C ?4 test result similar, its UL94 vertical combustion be only V ?2 grades, material hardness is increased to 96A by 90A.Meanwhile, not only hardness is higher for its extrusion electric wire, and surface irregularity, only 6.5Mpa of electric wire intensity, and elongation at break only 98%, has lost the use value as charging electric motor vehicles electric wire.
Comparative example C ?6: on the basis of embodiment 3, only change the kind of base material, by the TPV of equivalent replace above-mentioned TPE ?S base material, keep composition and the constant rate of other each component.Test result from comparative example C ?6 in table 6: compared with embodiment 3 results, its flame retardant properties remains unchanged, and heat aging performance is slightly improved.But its tensile strength declines obviously, and extrusion electric wire intensity only has 7.8Mpa, does not reach the 8.5Mpa lower limit requirement that UL standard specifies, can not use as charging electric motor vehicles electric wire.
Embodiment 4: on the basis of embodiment 3, only change the composition of part base material: adopt 50 parts of POP ?3980 replace 40 parts of PP ?R370Y and 10 parts of N250 white oils, keep composition and the constant rate of other each component.The test result of embodiment 4 in table 4: compared with embodiment 3, the hardness of matrix material is reduced to 85A by 90A, and elongation at break increases to 565% by 468%, and electric wire flexibility increases, all other performances remain unchanged substantially, meet the use of charging electric motor vehicles electric wire.
Embodiment 5: on the basis of embodiment 3, only change the composition of part base material: adopt 60 parts of POP ?3980 replace 40 parts of PP ?R370Y and 20 parts of N250 white oils, reduce the interpolation umber (hexaphenoxycyclotriphosphazene and MDH H7C/2 are reduced to 40 parts by 45 parts respectively) of fire retardant simultaneously, keep composition and the constant rate of other each component.Table 4 embodiment 5 test results: compared with embodiment 3, composite hardness is reduced to 84A by 90A, elongation at break increases to 583% by 468%, electric wire flexibility obviously increases, intensity is slightly improved simultaneously, and other performance variation is little, and its over-all properties is further improved generally.
Comparative example E ?1: on the basis of embodiment 5, only change the kind of fire retardant MDH, adopt the MDH H7 (MDH ?I) of equivalent long time without surface modification to substitute MDH H7C/2 (MDH ?II), composition and the ratio of other each component remain unchanged.Table 6 comparative example E ?1 test result: compared with embodiment 5, the mechanical property of matrix material and flame retardant properties all to some extent decline, UL94 test result V ?1 grade; Electric wire surface is slightly coarse, occur inhomogeneous gel particle distribution, UL1581 flame retardant test FT ?2 grades, do not reach desirable charging electric motor vehicles electric wire standard.
Comparative example E ?2: on embodiment 5 bases, change part base material composition, with the POP of 10 parts ?3980 replace the N250 white oil of 10 parts, reduce the addition of fire retardant: hexaphenoxycyclotriphosphazene and MDH H7C/2 are reduced to 35 parts by 40 parts respectively simultaneously.Table 6 comparative example E ?2 test results: with embodiment 5 and comparative example E ?1 compare, matrix material and extrusion electric wire mechanical property all increase to some extent, but flame retardant properties all obviously reduces, UL94 and UL1581 flame retardant test Fail, flame retardant properties does not meet the requirement of charging electric motor vehicles electric wire.
Comparative example E ?3: on embodiment 5 bases, only change the kind of part base material, with the POP of equivalent ?6202 replace POP ?3980, composition and the ratio of other each component remain unchanged.Table 6 comparative example E ?3 test results: compared with embodiment 5, composite hardness is reduced to 79A by 84A, simultaneously, electric wire intensity slightly declines, after thermal shock test, there is cracking phenomena, aging rear strength retention is 69% (≤75%) only, percent retention of elongation 63% (≤75%), and its over-all properties can not meet the service requirements of charging electric motor vehicles electric wire.
Comparative example E ?4: on the basis of embodiment 5, only remove anti-wear agent nanometer SiO2, keep other each component composition and constant rate.Table 6 comparative example E ?4 test results visible: after wear test, there is obvious scratch in electric wire surface, and as the use of charging electric motor vehicles electric wire, its wear resisting property is poor, and reduce work-ing life.
To sum up, can be found by table 4: a kind of TPE prepared by the present invention ?S base charging electric motor vehicles electric wire material there is good over-all properties.Its extrusion become line fire-retardant VW ?1 grade, ageing resistance excellence, without cracking and fire retardant separate out, can be at 105 DEG C of life-time service.As charging electric motor vehicles electric wire, its smooth surface, soft pliable song, wear resistance is good, can substitute traditional Halogen PVC base electric wire, meets well the service requirements of current charging electric motor vehicles electric wire.
Disclosed is above only the several specific embodiments of the present invention, but the application is not limited to this, any on basis of the present invention, and the variation that wherein fill a prescription composition, complete processing etc. are carried out, all should be within the application's protection domain.
Claims (7)
1. a charging electric motor vehicles electric wire material, is characterized in that: the raw material by weight components is made:
100 parts of plasticity-elasticity soft materials
50～300 parts of white oils
50～200 parts of polyolefine materials
50～200 parts of Halogenless composite fire retardants
0～20 part of char-forming agent
0～3 part of smoke suppressant
0.5～1.0 part, oxidation inhibitor
0.3～3.0 part of lubricant
2～8 parts of anti-wear agents
0～2.0 part of coupling agent
0～5 part of expanding material.
2. charging electric motor vehicles electric wire material according to claim 1, it is characterized in that: described plasticity-elasticity soft material is Powdered hydrogenation (styrene-butadiene-styrene) segmented copolymer, its molecular weight is 8～280,000, the ratio of phenylethylene/butadiene be 2:8 to 4:6, density is 0.85～0.95; The technical grade paraffin oil of described white oil for obtaining in petroleum cracking process, flash-point is 200～250 DEG C, kinematic viscosity is 30～150cSt at 40 DEG C.
3. charging electric motor vehicles electric wire material according to claim 1 and 2, is characterized in that: described polyolefine material is that the one in polyethylene, polypropylene, ethylene-octene random copolymers, ethylene-propylene random copolymer is several; Described Halogenless composite fire retardant is super fine magnesium hydroxide, aluminium hydroxide, hydrated magnesium silicate or the potter's clay of organic modification of surface and the mixture of ammonium polyphosphate, melamine salt, polyphosphonitrile or phosphoric acid ester.
4. charging electric motor vehicles electric wire material according to claim 3, is characterized in that: described polyphosphonitrile is that phosphonium flame retardant is phenoxy group polyphosphonitrile.
5. charging electric motor vehicles electric wire material according to claim 1 and 2, is characterized in that: char-forming agent is polycarbonate, polyhenylene ether, epoxy resin or resol.
6. charging electric motor vehicles electric wire material according to claim 1 and 2, is characterized in that: smoke suppressant is zinc borate, ammonium octamolybdate, molybdenum dioxide or stannic oxide; Described oxidation inhibitor is the binary mixture of antioxidant 1010 and irgasfos 168, anti-oxidant DLTP or oxidation inhibitor DSTP; Described lubricant is erucicamide, amine hydroxybenzene or stearic amide; Described anti-wear agent is the nano silicon of surface organic modification; Described coupling agent is silane coupling agent; Described expanding material is the polyethylene of ethylene-vinyl acetate copolymer, maleic anhydride graft, the polypropylene of maleic anhydride graft, ethylene-octene copolymer, the ethylene-propylene copolymer of maleic anhydride graft or the hydrogenation of maleic anhydride graft (styrene-butadiene-styrene) segmented copolymer of maleic anhydride graft.
7. the preparation method of a charging electric motor vehicles electric wire material claimed in claim 1, it is characterized in that: 100 parts of plasticity-elasticity soft materials and 50～300 parts of white oils are added in mixing machine, stir and within 3～5 minutes, make white oil by full and uniform absorption, then 50～200 parts of polyolefine materials, 50～200 parts of Halogenless composite fire retardant, 0～20 part of char-forming agent, 0～3 part of smoke suppressant, 0.5～1.0 part of oxidation inhibitor, 0.3～3.0 part of lubricant, 2～8 parts of anti-wear agents, 0～2.0 part of coupling agent, 0～5 part of expanding materials through activation treatment are added in mixing machine and mixed successively; The good material of mixture is transferred to reactive twin screw extruder hopper, and melt blending extruding pelletization under 150～250 DEG C of processing temperatures, obtains product.
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