CN117924914B - Special cable for automobile electric side sliding door and preparation process thereof - Google Patents
Special cable for automobile electric side sliding door and preparation process thereof Download PDFInfo
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- CN117924914B CN117924914B CN202410330194.5A CN202410330194A CN117924914B CN 117924914 B CN117924914 B CN 117924914B CN 202410330194 A CN202410330194 A CN 202410330194A CN 117924914 B CN117924914 B CN 117924914B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
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- 239000012779 reinforcing material Substances 0.000 claims abstract description 14
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 29
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- 238000003756 stirring Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
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- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
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- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QDYBCIWLGJMJGO-UHFFFAOYSA-N dinitromethanone Chemical group [O-][N+](=O)C(=O)[N+]([O-])=O QDYBCIWLGJMJGO-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- NDRPHZPVTSFYLH-UHFFFAOYSA-N 2,4,6-tris(2-butoxyphenyl)-1,3,5-triazine Chemical compound C(CCC)OC1=C(C=CC=C1)C1=NC(=NC(=N1)C1=C(C=CC=C1)OCCCC)C1=C(C=CC=C1)OCCCC NDRPHZPVTSFYLH-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a special cable for an electric side sliding door of an automobile and a preparation process thereof, which belong to the technical field of cable production and processing, wherein the special cable comprises a transmission line and a sheath coated outside the transmission line, and the sheath comprises the following raw materials in parts by weight: 45-65 parts of isocyanate; 30-75 parts of polyalcohol; 3-15 parts of cross-linking agent; 15-30 parts of TPE elastomer; 1-15 parts of modified carbon nanomaterial; 0.5-6 parts of light stabilizer; 2-7 parts of pigment; wherein, the surface of the modified carbon nanomaterial is grafted with oxygen-containing functional groups. The special cable designed by the invention has small volume and does not occupy too much automobile space; the raw materials, the preparation process and the like of the sheath are designed, and the performances of the matrix polymer material and the reinforcing material are utilized, so that the sheath has higher bending resistance and low-temperature brittle failure resistance, and can meet the actual application requirements.
Description
Technical Field
The invention belongs to the technical field of cable production and processing, and particularly relates to a cable special for an electric side sliding door of an automobile and a preparation process of the cable.
Background
In most of current middle-high-end MPV motorcycle types, generally all use and have electric side sliding door, when using, the driver and passenger only need press the button or start the action of opening and closing the door, and the signal is transmitted to the automobile control end through the cable, and the automobile control end rethread cable sends out the order and can control electric side sliding door's opening or closing, and it is very convenient when using.
The electric side sliding door needs to be connected with the automobile body through a cable, a power supply and a control signal are transmitted, the electric side sliding door can do reciprocating motion relative to the automobile body when being opened and closed, the cable can be bent in a U shape, and the electric side sliding door needs to be frequently opened and closed in the using process of the automobile, so that higher requirements are provided for bending resistance of the cable. In addition, the cable includes a plurality of independent transmission lines for transmitting different signals, and how to combine the plurality of independent cables together is a problem.
The current mainstream cable design scheme mainly has the following two kinds: the first is a japanese design scheme, in which a plurality of cables are fixed together to form a whole by adopting a wire arranging process, but the whole cable obtained by adopting the wire arranging process has poor structural strength and bending resistance, and the finally obtained cable has poor appearance design sense and does not accord with the positioning of middle-high-end automobiles. The second is the germany scheme, directly places many cables in the tank chain, through the reciprocating motion of tank chain cable, can avoid the poor problem of cable itself bending resistance, but tank chain volume is great, can occupy the interior space to the input cost of tank chain is higher.
And the cable for the electric side sliding door is arranged below the vehicle door and connected between the vehicle body and the electric side sliding door, when the electric side sliding door is closed, the cable is hidden in a gap between the vehicle body and the vehicle door, and when the electric side sliding door is opened, the cable is exposed outside and belongs to an exposed piece, and according to the temperature of the vehicle in different areas, the high-low temperature brittle failure resistance and the like of the cable are needed to be considered.
Therefore, a special cable for the electric side sliding door needs to be designed to solve the technical problems in the prior art.
Disclosure of Invention
The invention aims to provide a special cable for an electric side sliding door of an automobile and a preparation process thereof, so as to solve the technical problems in the background art.
In order to achieve the above purpose, the invention discloses a special cable for an electric side sliding door of an automobile, which comprises a transmission line and a sheath coated outside the transmission line, wherein the sheath comprises the following raw materials in parts by weight:
45-65 parts of isocyanate;
30-75 parts of polyalcohol;
3-15 parts of cross-linking agent;
15-30 parts of TPE elastomer;
1-15 parts of modified carbon nanomaterial;
0.5-6 parts of light stabilizer;
2-7 parts of pigment;
wherein, the surface of the modified carbon nanomaterial is grafted with oxygen-containing functional groups.
Further, the raw material of the sheath also comprises 3-10 parts of organic reinforcing fibers, wherein the organic reinforcing fibers comprise aramid fibers and/or PBO fibers.
Further, the raw materials of the sheath also comprise 25-35 parts of PIB.
Further, the TPE elastomer comprises one or more of TPU, TPEE, TPV and TPO.
Further, the preparation method of the modified carbon nanomaterial comprises the following steps: adding carboxylated carbon nanotubes and graphene oxide into an aqueous solution of a silane coupling agent, uniformly dispersing by ultrasonic, performing suction filtration, vacuum drying a filter cake, and then heating, melting and mixing with isocyanate to obtain the modified carbon nanomaterial.
Further, the oxygen-containing functional group comprises one or more of carboxyl, hydroxyl, phenolic hydroxyl, anhydride, nitro, ketone group, ester group and carbonyl.
Further, the PIB has a molecular weight of 10 3-4×104; the viscosity at 100℃was 3X 10 2-7×105 mPas.
Further, the special cable of the electric side sliding door of the automobile is of a flat crawler type structure, embossing stripes are arranged outside the special cable, the special cable comprises a sheath and a plurality of independent transmission lines which are arranged in the sheath side by side, and each transmission line comprises a conductor located on a core layer and an insulating layer coated outside the core layer.
The invention also claims a preparation process of the special cable for the electric side sliding door of the automobile, which comprises the following steps:
(1) Sequentially adding TPE elastomer, isocyanate, polyol and cross-linking agent into a reaction kettle, and uniformly stirring and mixing;
(2) Sequentially adding the modified carbon nanomaterial, the light stabilizer and the pigment, and stirring and mixing uniformly;
(3) And extruding and coating the melt outside the transmission line by adopting a melt extrusion process, and cooling, solidifying and forming.
Further, in the step (4), cooling, solidifying and forming are completed in two steps, and when the first step of cooling, solidifying and forming reaches 40-60%, embossing is performed on the outer part of the sheath to form embossing stripes; and then cooling and solidifying in the second step until the sheath is completely cooled, solidified and formed.
Compared with the prior art, the special cable for the electric side sliding door of the automobile and the preparation process thereof have the following advantages: the special cable is formed by directly melting and extruding the outer parts of the transmission lines to form the sheath, and the transmission lines are arranged side by side, so that the special cable has small volume and does not occupy excessive automobile space; the sheath with high mechanical strength is obtained by designing the raw materials, the preparation process and the like of the sheath and utilizing the performances of the matrix polymer material and the reinforcing material, and has higher bending resistance and low-temperature brittle failure resistance.
Drawings
Fig. 1: the invention discloses a three-dimensional structure schematic diagram of a cable special for an electric side sliding door of an automobile.
Fig. 2: the invention discloses a cross section structure schematic diagram of a special cable for an electric side sliding door of an automobile.
Wherein, 1, the sheath; 2. a conductor; 3. an insulating layer; 4. embossing the stripes.
Detailed Description
The three-dimensional structure schematic diagram and the cross-section structure schematic diagram of the cable special for the electric side sliding door of the automobile are shown in fig. 1 and 2, the cable is of a flat crawler type structure, embossing stripes 4 are arranged outside the cable, the cable special for the electric side sliding door of the automobile comprises an outermost sheath 1 and a plurality of independent transmission lines arranged in the sheath 1 side by side, each transmission line consists of a conductor 2 positioned in a core layer and an insulating layer 3 coated outside the core layer, the flat crawler type structure is beneficial to arranging the plurality of independent transmission lines side by side, and the embossing stripes 4 outside the cable can improve the anti-skid performance of the cable and improve the design sense of the cable. The type and use of the transmission line in relation to the control system of the electric vehicle itself is not within the scope of the invention, and only one exemplary version is given here and will not be repeated.
In the opening and closing process of the electric side sliding door, the sheath plays a role in protecting the transmission line, absorbs and buffers external force, and prevents the transmission line from being damaged in the reciprocating bending process by utilizing the high bending resistance of the sheath.
In order to meet the use requirement, the invention provides a special cable for an electric side sliding door of an automobile, which comprises a transmission line and a sheath coated outside the transmission line, wherein the sheath comprises the following raw materials in parts by weight:
45-65 parts of isocyanate;
30-75 parts of polyalcohol;
3-15 parts of cross-linking agent;
15-30 parts of TPE elastomer;
1-15 parts of modified carbon nanomaterial;
0.5-6 parts of light stabilizer;
2-7 parts of pigment;
Wherein, the surface of the modified carbon nano material is grafted with oxygen-containing functional groups, and the oxygen-containing functional groups comprise one or more of carboxyl, hydroxyl, phenolic hydroxyl, anhydride, nitro, ketone group, ester group and carbonyl.
In a preferred embodiment, the raw material of the sheath further comprises 3-10 parts of organic reinforcing fibers, including aramid fibers and/or PBO fibers; in another preferred embodiment, the raw material of the sheath further comprises 25-35 parts PIB, wherein the PIB has a molecular weight of 10 3-4×104; the viscosity at 100℃was 3X 10 2-7×105 mPas.
Wherein, the isocyanate can be Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI) and the like.
The polyol can be selected from polyoxypropylene glycol, polyoxypropylene triol, pentaerythritol, xylitol, sorbitol, mannitol, sucrose, tetrahydrofuran polyether, polyethylene glycol adipate glycol, poly epsilon-caprolactone polyol, polycarbonate glycol and the like.
The cross-linking agent is selected from peroxide cross-linking agent, and specifically selected from bis (2, 4-dichlorobenzoyl) peroxide, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane, tert-butyl peroxy-2-ethylhexyl carbonate, dicumyl peroxide, benzoyl peroxide and the like.
The light stabilizer is selected from ultraviolet absorbent including salicylate, benzophenone, benzotriazole, substituted acrylonitrile, triazine, etc., specifically selected from phenyl o-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, resorcinol monobenzoate, 2' -thiobis (4-tert-octylphenoloxy) nickel, tris (1, 2, 6-pentamethylpiperidyl) phosphite, 4-benzoyloxy-2, 6-tetramethylpiperidine, 2,4, 6-tris (2 ' n-butoxyphenyl) -1,3, 5-triazine, hexamethylphosphoric triamide, etc.
Carbon black can be used as pigment.
The preparation method of the modified carbon nanomaterial comprises the following steps: adding carboxylated carbon nanotubes and graphene oxide into an aqueous solution of a silane coupling agent, uniformly dispersing by ultrasonic, performing suction filtration, vacuum drying a filter cake, and then heating, melting and mixing with isocyanate to obtain the modified carbon nanomaterial.
The carbon nano tube is a one-dimensional nano material, the graphene oxide is a two-dimensional nano material, the two are carbon materials, carboxyl groups, hydroxyl groups and other groups are grafted on the surface of the carboxylated carbon nano tube, hydroxyl groups, carboxyl groups, amino groups and other groups are grafted on the surface of the graphene oxide, and hydrogen bonds are formed on the surfaces of the two nano carbon materials with different dimensions to form firm connection; the silane coupling agent can be selected from alkoxy silane coupling agent, amino silane coupling agent, epoxy silane coupling agent, etc., and specifically one or more of A-151, A-171, A-172, KH550, KH560 and KH570 can be selected; the silane coupling agent can form connection between the inorganic interface of the nano carbon material and the organic interface of the isocyanate, so that the nano carbon material can be more uniformly and effectively dispersed in the isocyanate and form chemical bonding with the isocyanate, thereby being more beneficial to the uniform dispersion of the nano carbon material in the sheath and preventing migration of the nano carbon material.
The preparation process of the cable special for the electric side sliding door of the automobile comprises the following steps of:
(1) Sequentially adding TPE elastomer, isocyanate, polyol and cross-linking agent into a reaction kettle, and uniformly stirring and mixing;
(2) Sequentially adding the modified carbon nanomaterial, the light stabilizer and the pigment, and stirring and mixing uniformly;
(3) And extruding and coating the melt outside the transmission line by adopting a melt extrusion process, and cooling, solidifying and forming.
In the step (3), cooling, solidifying and forming are completed in two steps: the first step is to emboss the outside of the sheath to form embossed stripes when cooling, solidifying and forming to 40-60%; and then cooling and solidifying in the second step until the sheath is completely cooled, solidified and formed.
In a specific embodiment, when the raw material of the sheath further comprises 3-10 parts of organic reinforcing fibers, it is added to the reaction system in step (2).
In another specific embodiment, when 25-35 parts PIB is included in the raw material of the jacket, the preparation process is as follows:
(1) Adding TPE elastomer and partial PIB into a reaction kettle, heating, stirring and mixing uniformly;
(2) Sequentially adding isocyanate, polyol and cross-linking agent into the reaction kettle, and uniformly stirring and mixing;
(3) Heating and melting the balance PIB in advance, sequentially adding the modified carbon nano material and the organic reinforcing fiber (if any), and uniformly stirring and mixing to obtain a reinforcing material melt; then adding the mixture into the melt in the step (2), and stirring and mixing the mixture again to be uniform;
(4) And extruding and coating the melt outside the transmission line by adopting a melt extrusion process, and cooling, solidifying and forming.
In the step (4), cooling, solidifying and forming are completed in two steps, specifically, when the cooling, solidifying and forming is carried out in the first step to 40-60%, embossing is carried out on the outer part of the sheath, and embossing stripes are formed; and then cooling and solidifying in the second step until the sheath is completely cooled, solidified and formed.
The molecular weight of PIB is 10 3-4×104; the viscosity at 100℃was 3X 10 2-7×105 mPas. PIB has high tackiness, and can bond various raw materials together, and PIB with low molecular weight and high viscosity is selected here, so that the tackiness can be exerted more effectively. The TPE elastomer comprises one or more of TPU, TPEE, TPV and TPO. The TPE elastomer has the plasticity of plastics and the high elasticity of rubber, and has high melt index and high viscosity, so that the TPE elastomer can be better combined with PIB, the agglomeration of the PIB can be prevented, and the PIB can fully exert the adhesiveness of the PIB; the high elasticity of TPE can give the sheath higher elasticity, can absorb the effort from outside, avoid inside transmission line damage and ensure sheath structural integrity. Firstly, TPE elastomer and PIB are uniformly mixed, so that the respective performances of the TPE elastomer and the PIB can be fully exerted.
And adding the modified carbon nanomaterial and the organic reinforcing fiber into the molten PIB in sequence, and covering the PIB on the surfaces of the modified carbon nanomaterial and the organic reinforcing fiber, so that the adhesiveness of the modified carbon nanomaterial and the organic reinforcing fiber is improved, and the modified carbon nanomaterial and the organic reinforcing fiber are ensured to be more uniformly dispersed in the resin matrix of the sheath.
PIB is added twice, so that the stirring and mixing time can be reduced, the materials are easier to mix uniformly, and the materials are ensured to be more uniform and consistent.
The surface of the modified carbon nano material is also coated with isocyanate, the isocyanate and the polyol are crosslinked and cured under the action of a crosslinking agent to obtain polyurethane which is a matrix of the sheath, and in the crosslinking and curing process of the polyurethane, a molecular chain is penetrated and crosslinked with the molecular chains of PIB and TPE to form a multiple interpenetrating network structure, so that the sheath is endowed with higher strength.
In the isocyanate crosslinking process of the surface coating of the modified carbon nanomaterial, an organic layer is formed on the surface of the carbon nanomaterial, and the uniform dispersion of the modified carbon nanomaterial in the resin matrix is further promoted.
Since the organic reinforcing fiber is an organic component, the organic reinforcing fiber has better basic compatibility with resin.
The size of the organic reinforced fiber is in a micron level or a millimeter level, and the carbon nano material is in a nano level, so that multi-layer lap joint can be formed, the multi-layer lap joint can be combined with a multi-interpenetrating network structure of the resin matrix, the microstructure of the sheath is enriched, and the mechanical property, particularly the bending resistance, of the sheath is improved.
The insulating layer outside the transmission line is generally made of PE, PP, PET, PU resin materials, and is similar to the jacket provided by the invention, so that the jacket can be firmly adhered to the outer surface of the insulating layer in the process of melt extrusion, and the transmission line is protected.
The technical scheme of the invention is explained in detail by specific examples and comparative examples.
The parts mentioned hereinafter, unless otherwise indicated, refer to parts by mass.
Example 1
1. Preparing the modified carbon nanomaterial.
Dissolving a silane coupling agent KH550 in water, uniformly mixing to obtain a water solution with the concentration of 3%, adding 25 parts of carboxylated carbon nanotubes and 25 parts of graphene oxide into the water solution of KH550, and uniformly dispersing by ultrasonic waves; then carrying out suction filtration, and carrying out vacuum drying on the filter cake; and mixing the dried carbon nanomaterial with 10 parts of toluene diisocyanate, and heating, melting and mixing to obtain the modified carbon nanomaterial.
2. Preparing a reinforcing material melt.
And heating and melting 20 parts of PIB at 60 ℃, sequentially adding 8 parts of modified carbon nano material and 6 parts of aramid fiber, and heating, mixing and stirring uniformly to obtain a reinforcing material melt.
3. The preparation of the cable special for the electric side sliding door of the automobile comprises the following steps:
(1) Adding 25 parts of TPU (purchased from Shanghai Guangyi chemical industry Co., ltd.) and 10 parts of PIB into a reaction kettle, heating to 95-100 ℃, and stirring and mixing uniformly;
(2) Sequentially adding 48 parts of toluene diisocyanate, 50 parts of polyethylene glycol adipate glycol (purchased from Xuzhou Peizhen new materials Co., ltd., model 1000 or 2000) and 8 parts of bis (2, 4-dichlorobenzoyl) peroxide into a reaction kettle, and stirring and mixing uniformly;
(3) Adding the reinforcing material melt, 3 parts of light stabilizer 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts of carbon black into the reaction kettle in the step (2), and stirring uniformly again;
(4) Extruding and cladding the melt obtained in the step (3) outside a transmission line by adopting a melt extrusion process at the temperature of 80-85 ℃, and cooling and solidifying by water, wherein the cooling and solidifying by water is carried out in two steps: the first step, embossing the outer part of the sheath to form embossed stripes when cooling, solidifying and forming to 50%; and a second step of: and continuing water cooling, cooling and solidifying until the sheath is completely cooled, solidified and formed.
Example 2
In contrast to example 1, no PIB was added to the raw material of the sheath. The amounts of the raw materials and the preparation methods of the special cables are shown in table 1.
Wherein the TPEE used in example 2 was purchased from jeers flame retardant chemical company, hangzhou, and the polyethylene glycol adipate diol was purchased from zernike new materials, inc, model 1000 or 2000.
Example 3
In contrast to example 1, no organic reinforcing fibers were added to the raw materials of the sheath. The amounts of the raw materials and the preparation methods of the special cables are shown in table 1.
Among them, TPO used in example 3 was purchased from Shanghai, new Material technologies Co., ltd, and pentaerythritol was purchased from Hubei, chemical industry Co., ltd, industrial grade.
Example 4
In contrast to example 1, no PIB and no organic reinforcing fibers were added to the raw materials of the jacket. The amounts of the raw materials and the preparation methods of the special cables are shown in table 1.
Wherein the TPU used in example 4 was purchased from Shanghai Guangyi chemical Co., ltd., tetrahydrofuran polyether was purchased from Jining Hua Kai resin Co., ltd., specification PTMG-650 or PTMG-800, product number L50916.
Example 5
Compared with the embodiment 1, PIB is not added into the raw materials of the sheath, the preparation process of the cable is changed, and the cable is prepared by adopting a one-pot method. The amounts of the raw materials and the preparation methods of the special cables are shown in table 1.
Among them, the TPU used in example 5 was purchased from Shanghai Guangyi chemical Co., ltd, and the polyoxypropylene triol was purchased from Shandong Mole chemical Co., ltd, model K12.
Comparative example 1
The preparation of the cable special for the electric side sliding door of the automobile comprises the following steps:
(1) Sequentially adding 30 parts of toluene diisocyanate, 80 parts of polyol, 20 parts of cross-linking agent, 3 parts of light stabilizer and 6 parts of carbon black into a reaction kettle, heating to 90 ℃, and stirring and mixing uniformly;
(2) And (5) melt extrusion, cooling and solidifying.
The cable structures, the respective raw material types and the main preparation processes in the above examples 1 to 5 and comparative example 1 are shown in table 1.
Among them, the TPU used in comparative example 1 was purchased from Shanghai Guangyi chemical Co., ltd, and the polyoxypropylene glycol was purchased from Shandong Baihong New Material Co., ltd, cat. Number 020.
Table 1 summary of raw material composition of sheath of dedicated cable and cable preparation process in examples 1 to 6 and comparative example 1
| Numbering device | Raw materials | Cable preparation process |
| Example 1 | 48 Parts of isocyanate, 50 parts of polyol, 8 parts of cross-linking agent, 30 parts of PIB, 25 parts of TPU, 8 parts of modified carbon nanomaterial, 6 parts of aramid fiber, 3 parts of light stabilizer and 5 parts of carbon black. | 1. Preparing a modified carbon nanomaterial: comprises 25 parts of carboxylated carbon nano-tubes and 25 parts of graphene oxide, and is added into 3wt% of KH550 aqueous solution, and is heated, melted and mixed with 10 parts of toluene diisocyanate after treatment. 2. Preparing a reinforcing material melt: 8 parts of modified carbon nano material and 6 parts of aramid fiber are sequentially added into 20 parts of PIB melt, and uniformly stirred and mixed. 3. Preparing a special cable: (1) heating, stirring and uniformly mixing 25 parts of TPU and 10 parts of PIB; (2) 48 parts of toluene diisocyanate, 50 parts of polyethylene glycol adipate glycol and 8 parts of cross-linking agent bis (2, 4-dichlorobenzoyl) peroxide are added; (3) Adding a reinforcing material melt, 3 parts of light stabilizer 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 5 parts of carbon black; (4) melt extrusion, cooling, solidifying and embossing treatment. |
| Example 2 | 52 Parts of isocyanate, 50 parts of polyol, 10 parts of cross-linking agent, 20 parts of TPEE, 10 parts of modified carbon nanomaterial, 9 parts of PBO fiber, 2 parts of light stabilizer and 4 parts of carbon black. | 1. Preparing a modified carbon nanomaterial: comprises 15 parts of carboxylated carbon nano-tubes and 25 parts of graphene oxide, and is added into 3wt% of KH560 aqueous solution, and is heated, melted and mixed with 12 parts of diphenylmethane diisocyanate after treatment. 2. Preparing a special cable: (1) Adding 20 parts of TPEE, 52 parts of toluene diisocyanate, 50 parts of polyethylene glycol adipate glycol and 10 parts of cross-linking agent bis (2, 4-dichlorobenzoyl) peroxide into a reaction kettle, and uniformly mixing and stirring; (2) 10 parts of modified carbon nanomaterial, 9 parts of PBO fiber, 2 parts of light stabilizer 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorinated benzotriazole and 4 parts of carbon black are sequentially added; (3) melt extrusion, cooling, solidifying and embossing treatment. |
| Example 3 | 50 Parts of isocyanate, 65 parts of polyol, 8 parts of cross-linking agent, 35 parts of PIB, 25 parts of TPO, 9 parts of modified carbon nanomaterial, 5 parts of light stabilizer and 7 parts of carbon black. | 1. Preparing a modified carbon nanomaterial: comprises 18 parts of carboxylated carbon nano-tubes and 20 parts of graphene oxide, and is added into 3wt% of KH570 water solution, and is heated, melted and mixed with 10 parts of hexamethylene diisocyanate after treatment. 2. Preparing a reinforcing material melt: and sequentially adding 9 parts of modified carbon nano materials into 18 parts of PIB melt, and uniformly stirring and mixing. 3. Preparing a special cable: (1) heating, stirring and uniformly mixing 25 parts of TPO and 17 parts of PIB; (2) 50 parts of hexamethylene diisocyanate, 65 parts of pentaerythritol and 8 parts of cross-linking agent tert-butyl peroxy-2-ethylhexyl carbonate are added; (3) Adding a reinforcing material melt, 5 parts of light stabilizer 2-hydroxy-4-n-octoxybenzophenone and 7 parts of carbon black; (4) melt extrusion, cooling, solidifying and embossing treatment. |
| Example 4 | 60 Parts of isocyanate, 60 parts of polyol, 6 parts of cross-linking agent, 18 parts of TPU, 9 parts of modified carbon nanomaterial, 6 parts of light stabilizer and 7 parts of carbon black. | 1. Preparing a modified carbon nanomaterial: comprises 25 parts of carboxylated carbon nano-tubes and 22 parts of graphene oxide, and is added into 3.5wt% of KH550 aqueous solution, and is heated, melted and mixed with 15 parts of toluene diisocyanate after treatment. 2. Preparing a special cable: (1) Heating, stirring and uniformly mixing 18 parts of TPU, 60 parts of toluene diisocyanate, 60 parts of tetrahydrofuran polyether and 6 parts of cross-linking agent benzoyl peroxide; (2) Adding 9 parts of modified carbon nanomaterial, 6 parts of light stabilizer resorcinol monobenzoate and 7 parts of carbon black; (3) melt extrusion, cooling, solidifying and embossing treatment. |
| Example 5 | 51 Parts of isocyanate, 50 parts of polyol, 9 parts of cross-linking agent, 28 parts of TPU, 6 parts of modified carbon nanomaterial, 7 parts of PBO fiber, 2 parts of light stabilizer and 4 parts of carbon black. | 1. Preparing a modified carbon nanomaterial: comprises 20 parts of carboxylated carbon nano-tubes and 15 parts of graphene oxide, and is added into 3wt% of KH560 aqueous solution, and is heated, melted and mixed with 11 parts of toluene diisocyanate after treatment. 2. Preparing a special cable: (1) 28 parts of TPU, 51 parts of toluene diisocyanate, 50 parts of polyoxypropylene triol, 9 parts of crosslinking agent dicumyl peroxide, 6 parts of modified carbon nanomaterial, 7 parts of PBO fiber, 2 parts of light stabilizer 2, 4-dihydroxybenzophenone and 4 parts of carbon black are sequentially added into a reaction kettle; (2) melt extrusion, cooling, solidifying and embossing treatment. |
| Comparative example 1 | 30 Parts of isocyanate, 80 parts of polyol, 20 parts of cross-linking agent, 3 parts of light stabilizer and 6 parts of carbon black. | (1) Sequentially adding 30 parts of isophorone diisocyanate, 80 parts of polyoxypropylene glycol, 20 parts of cross-linking agent 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane, 3 parts of light stabilizer 2-hydroxy-4-methoxybenzophenone and 6 parts of carbon black into a reaction kettle, heating to 90 ℃, stirring and mixing uniformly; (2) melt extrusion, cooling and solidifying. |
Performance test:
and detecting the U-shaped bending performance and the high-low temperature brittle failure performance.
(1) U-shaped bending performance test: the repeated bending test machine is adopted for experiments, the temperature is 21-27 ℃, the relative humidity is 45-75% RH, the sample width is 225mm plus or minus 5mm, the bending angle is 0-180 degrees, the bending radius is 0-18mm, the moving stroke is 0-60mm, the reciprocating speed is 10-120 cycles/min, the test times are 10- 8, and the sample shape is observed.
(2) High-low temperature brittle failure performance test: the experiment is carried out in a high-low temperature box, the temperature is kept at 75 ℃ for 2 hours, then the temperature is reduced from 75 ℃ to-50 ℃ in 0.5 hours, the temperature is kept for 2 hours, the temperature is increased from-50 ℃ to 75 ℃ in 0.5 hours, and the cycle is carried out for 30 times. And then taking out the sample, and carrying out appearance observation and U-shaped bending performance test.
The test results are shown in Table 2.
TABLE 2 Performance test results of the dedicated cables obtained in examples 1 to 5 and comparative example 1
| Numbering device | U-shaped bending property | High and low temperature brittle failure performance |
| Example 1 | No crack | No crack and no break after U-shaped bending performance test |
| Example 2 | No crack | No crack and no break after U-shaped bending performance test |
| Example 3 | No crack | No crack and no break after U-shaped bending performance test |
| Example 4 | No crack | No crack exists, and the sample has fine cracks after the U-shaped bending performance test |
| Example 5 | No crack | No crack exists, and the sample has fine cracks after the U-shaped bending performance test |
| Comparative example 1 | Fracture of | Sample brittle failure, failure to perform U-shaped bending performance test |
Therefore, the cable special for the electric side sliding door of the automobile, which is obtained by adopting the method, has higher U-shaped bending resistance and high-low temperature brittle fracture resistance, can be suitable for repeated cyclic and reciprocating opening and closing of the electric side sliding door, has long service life, has good high-low temperature resistance when being used in areas with different temperatures, has no obvious reduction in performance, and can meet the actual application requirements.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the invention, but any modifications, equivalent substitutions, improvements, etc. within the design concept of the present invention should be included in the scope of the present invention.
Claims (7)
1. The utility model provides a special cable of electronic sideslip door of car, includes the transmission line and cladding in the outside sheath of transmission line, its characterized in that: the sheath comprises the following raw materials in parts by mass:
45-65 parts of isocyanate;
30-75 parts of polyalcohol;
3-15 parts of cross-linking agent;
15-30 parts of TPE elastomer;
1-15 parts of modified carbon nanomaterial;
0.5-6 parts of light stabilizer;
2-7 parts of pigment;
wherein, the surface of the modified carbon nano material is grafted with oxygen-containing functional groups;
The preparation method of the modified carbon nanomaterial comprises the following steps: adding carboxylated carbon nanotubes and graphene oxide into an aqueous solution of a silane coupling agent, uniformly dispersing by ultrasonic, performing suction filtration, vacuum drying a filter cake, and then heating, melting and mixing with isocyanate to obtain a modified carbon nanomaterial;
the raw material of the sheath also comprises 3-10 parts of organic reinforcing fibers, wherein the organic reinforcing fibers comprise aramid fibers and/or PBO fibers;
The raw materials of the sheath also comprise 25-35 parts of PIB;
the preparation process of the cable special for the electric side sliding door of the automobile comprises the following steps of:
(1) Adding TPE elastomer and partial PIB into a reaction kettle, heating, stirring and mixing uniformly;
(2) Sequentially adding isocyanate, polyol and cross-linking agent into the reaction kettle, and uniformly stirring and mixing;
(3) Heating and melting the balance PIB in advance, and sequentially adding the modified carbon nano material and the organic reinforcing fiber to obtain a reinforcing material melt; adding the reinforcing material melt, the light stabilizer and the pigment into the reaction kettle in the step (2), and stirring uniformly again;
(4) And extruding and coating the melt outside the transmission line by adopting a melt extrusion process, and cooling, solidifying and forming.
2. The cable for electric side-sliding doors of automobiles according to claim 1, wherein: the TPE elastomer comprises one or more of TPU, TPEE, TPV and TPO.
3. The cable for electric side-sliding doors of automobiles according to claim 1, wherein: the oxygen-containing functional group comprises one or more of carboxyl, hydroxyl, phenolic hydroxyl, anhydride, nitro, keto, ester and carbonyl.
4. The cable for electric side-sliding doors of automobiles according to claim 1, wherein: the molecular weight of the PIB is 10 3-4×104; the viscosity at 100℃was 3X 10 2-7×105 mPas.
5. The cable for electric side-sliding doors of automobiles according to claim 1, wherein: the special cable for the electric side sliding door of the automobile is of a flat crawler type structure, embossing stripes are arranged outside the special cable, the special cable comprises a sheath and a plurality of independent transmission lines which are arranged in the sheath side by side, and each transmission line comprises a conductor located in a core layer and an insulating layer wrapping the outside of the core layer.
6. A process for preparing the cable special for the electric side sliding door of the automobile as claimed in any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
(1) Adding TPE elastomer and partial PIB into a reaction kettle, heating, stirring and mixing uniformly;
(2) Sequentially adding isocyanate, polyol and cross-linking agent into the reaction kettle, and uniformly stirring and mixing;
(3) Heating and melting the balance PIB in advance, and sequentially adding the modified carbon nano material and the organic reinforcing fiber to obtain a reinforcing material melt; adding the reinforcing material melt, the light stabilizer and the pigment into the reaction kettle in the step (2), and stirring uniformly again;
(4) And extruding and coating the melt outside the transmission line by adopting a melt extrusion process, and cooling, solidifying and forming.
7. The process of claim 6, wherein: in the step (4), the cooling, solidifying and forming are completed in two steps:
The first step is to emboss the outside of the sheath to form embossed stripes when cooling, solidifying and forming to 40-60%; and then cooling and solidifying in the second step until the sheath is completely cooled, solidified and formed.
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| CN117174359A (en) * | 2023-10-08 | 2023-12-05 | 广州恒星传导科技股份有限公司 | Light insulating cable for automobile and preparation process thereof |
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