CN102492320B - Quick-curing polyimide coating for high-temperature-resistant optical fiber - Google Patents
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Abstract
The invention discloses a quick-curing polyimide coating for high-temperature-resistant optical fiber. The quick-curing polyimide coating comprises an oligomer, a reactive diluent, a heat stabilizer and a reactive photoinitiator. According to the quick-curing polyimide coating for the high-temperature-resistant optical fiber, fluorinated chain segments and active acrylic acid chain segments are introduced into a polyimide structure, so that fluorine-modified photosensitive polyimide has excellent properties such as solubility, low optical loss, dielectric constant and moisture absorption; and the fluorine-modified photosensitive polyimide has higher photosensitivity, the film loss rate is minimal after film forming, and fundamental chains crosslink after being exposed, so that the chemical stability of the polymer is further improved. As a more complete polypyromellitimide structure is kept, the coating has special excellent thermal stability, good mechanical, electrical, chemical and photographic properties and very low coefficient of thermal expansion of polyimide. A pre-imidization technology is adopted, therefore, the processes of dehydration and condensation during the process of curing the polyimide are omitted; and the efficient reactive photoinitiator is introduced into the coating, and thus, the quick curing of the polyimide is realized.
Description
Technical field
The present invention relates to a kind of Quick-curing polyimide coating for high-temperature-resistant optical fiber, especially a kind of UV-light or electron beam cause can be quick-setting and have a Quick-curing polyimide coating for high-temperature-resistant optical fiber of heat resistance and stronger tensile strength.Be mainly used in the outer layer protection of extraordinary heatproof optical fiber cable, also can need quick-setting photoelectron paint field for other.
Background technology
The feature such as lightweight, anti-electromagnetic interference that optical fiber has, transmission capacity are large, gets more and more for aerospace signal transmission system.It is high temperature resistant, low temperature resistant etc. that severe Working environment requires optical fiber to have.Optical fiber coatings is for the protection of optical fibre, to exempt to be affected by the external environment, to keep the coating of its enough physical strength and optical property.The soft buffer layer of one deck applying during by fibre-optical drawing moulding, and the multilayer protection system that combines of the protective layer of the characteristic such as harder tough and tensile, the heatproof of the one deck applying afterwards, wear-resisting, chemicals-resistant.
The high-temperature resistant optical fiber working temperature that aviation is used is-55 ℃～200 ℃, fiber work temperature range-65 that space flight is used ℃～200 ℃.Conventional fiber coating working temperature is-55 ℃～85 ℃, and at present as the coating of optical fiber cable protection, the high-temperature resistant of acrylic coating is that 150 ℃, the maximum long term operation temperature of silicon rubber of thermofixation are 180 ℃.200 ℃ of external main polyimide that adopt of above heatproof optical fiber coatings.
Polyimide has good heatproof, media-resistant, resistent fatigue characteristic and excellent over-all properties.But as coating, generally the form with polyamic acid exists, and in solidification process, must pass through dehydrating condensation, this process of imidization.If imidization in advance, be difficult to dissolve, cause constructional difficulties, and thermofixation mode is difficult to realize fast setting, can not meet the needs of the quick wire drawing of optical fiber.
Light-sensitive polyimide (PSPI) is the nearly 30 years high-performance photosensitive resins that grow up, and has excellent thermostability, good machinery, electric, chemistry and photosensitive property.Owing to having sensitization and heat-resisting dual-use function concurrently, compare with non-photosensitive polyimide, there is curing speed feature faster, but general photosensitive polyimide resin is all to exist with polyamic acid form, the same with thermofixation polyimide, solidification process all be can't do without dehydration, this process of condensation imidization, if imidization in advance, solvability reduces greatly, is difficult to apply.
The present invention is based on above situation, in photo-sensistive polyimide resin, introduce fluoro-containing group, the fluorine modified light-sensitive polyimide forming has the performances such as good solvability, low optical losses, specific inductivity, water absorbability and refractive index, this type of PSPI has higher luminous sensitivity, film forming caudacoria rate of loss is minimum, because main chain after exposure is crosslinked, further improved thermostability and the chemical stability of polymkeric substance simultaneously.Such simple modified polyimide is due to active not enough, and curing speed can not meet the demands, and therefore also need in resin, introduce efficiency light initiator realizes fast setting.In photosensitive resin Light Curing, general light trigger does not participate in film formation reaction, and add-on too much can cause coating heat resistance can descend degradation disadvantage, we synthetic efficiency light initiator N-has the efficiency of initiation splendid to this photosensitive resin to methylbenzene maleimide, this initiator participates in film formation reaction, and there is good temperature tolerance, when guaranteeing that temperature tolerance and tensile strength do not reduce, realized fast setting.
Very many as CN1651533A, CN1047104, CN1047103, CN101792619A, CN101068852A etc. about ultraviolet curable optical fiber coating document and patent, but one piece of fast setting that relates to polyimide paint be there is no.The present invention has introduced active fluoro-containing group on polyimide segment, when making polyimide have photosensitivity, has good solubility, has introduced reactive high-efficiency light trigger and realized fast setting when keeping polyimide basic nature energy.
Summary of the invention
The object of the invention is to for the existing defect of polyimide paint, a kind of synthetic method and related application of the active light-sensitive polyimide polymkeric substance with new organic fluorine modification is provided.
Above-mentioned purpose of the present invention is achieved by following technical proposals: a kind of Quick-curing polyimide coating for high-temperature-resistant optical fiber, comprises active light-sensitive polyimide oligopolymer, reactive thinner, response type light trigger, thermo-stabilizer.The weight percent that each amounts of components accounts for coating total amount is active photosensitive oligomer 25 ~ 75%, reactive thinner 5 ~ 70%, response type light trigger 0.1 ~ 15%, thermo-stabilizer 0.1 ~ 10%.
Active light-sensitive polyimide oligopolymer is 2 of 10-35% by choosing mass percent, 2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa, 2,2-two (amino-4 aminomethyl phenyls of 3-)-HFC-236fa, 2,2-is two, and (4-is amino, phenyl) pyromellitic acid anhydride of any one in HFC-236fa and 10-30% or bibenzene tetracarboxylic dianhydride first synthesizing polyamides acid in the solvent of 25-75%, the imidization of dewatering again, finally adds the methacrylic chloride of 5-10% to be prepared from.Solvent is selected from dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
Response type light trigger is that N-is to methylbenzene maleimide.
Reactive thinner is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, vinylbenzene, three contracting four propylene glycol double methacrylates, two contracting propylene glycol double methacrylates, NVP, 1, one or more in 6-hexylene glycol double methacrylate.
Thermo-stabilizer is thiobisphenol, alkylidene bisphenols, alkylphenol, xenol compound, phosphite, phosphoric acid salt, one or more in organic amine.
The present invention makes polyimide have good solubility property by introduce fluoro-containing group in polyimide structures, introducing active crylic acid structure makes polyimide can realize photocuring, introduce reactive high-efficiency light trigger and realize the fast setting of photo-sensistive polyimide, and avoided normal starter residual disadvantage in coating, can be used as inner layer optical fiber paint, outer optical fiber coatings, special optical fiber coating, aerospace and use with heatproof radiation resistant optical fiber coating.
The preparation method of Quick-curing polyimide coating for high-temperature-resistant optical fiber of the present invention, mixes described active light-sensitive polyimide oligopolymer, response type light trigger, reactive thinner, thermo-stabilizer high-speed stirring, and sealing shading is preserved.
Concrete technology is:
(1) in three mouthfuls of reactors with agitating heater, adding mass percent is the pyromellitic acid anhydride (PMDA) of 10%-30%, 2 of 10%-35%, 2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa in 25-75%NMP, normal-temperature reaction 12 hours, synthesizing polyamides acid solution; Be warmed up to 150 ℃ to polyamic acid solution cyclodehydration imidization, obtain the fluorinated polyimide with activity hydroxy, this fluorine-containing imines powder has good solvability; Add 5%-10% methacrylic chloride at 10 ℃ of reaction 12-24 hour, the hydroxyl on acidylate PI-OH chain, is incorporated into acrylic acid structure on the side chain of polyimide molecule, obtains active photo-sensistive polyimide oligopolymer.
(2) in three mouthfuls of reactors of stirring are housed, introduce the maleic anhydride that mass percent is 18%-70%, add 20%-65% toluene and 5%-30% dimethyl formamide mixed solvent.The stopper MEHQ that finally adds reactant 0.05%-1%.Maleic anhydride is 53 ℃ of left and right stirring and dissolving, more slowly drips aniline with dropping funnel, and 3-5h drips off, and continues afterwards stirring reaction 0.5h, adds 0.05%-1% copper sulfate and tosic acid, is warming up to 150 ℃ and allows its backflow.Observe the water accumulating volume in water trap, observe and occur without the globule, can stop refluxing, return time is generally 2-6h left and right.Be cooled to 60 ℃, adding massfraction is 6% NaCO
3static layering, upper strata is toluene solution, lower floor is the aqueous solution.Upper solution being poured in the beaker that cold water is housed,, there is yellow needle crystal in predominate stirring on one side, then carries out suction filtration, washing, dry, just can obtain pure N-to methylbenzene maleimide.
(3) above-mentioned to obtain the weight percent that each amounts of components accounts for coating total amount be active light-sensitive polyimide oligopolymer 25-75%, reactive thinner 5-70%, response type light trigger 0.1-15%, thermo-stabilizer 0.1-10%.Can add appropriate reinforcing filler, after mixing in high-speed stirring, shading sealing is preserved if needed.
Feature of the present invention is, imidization before UV solidifies, the shrinking percentage of coating reduces greatly, can prevent that coating from chapping, and can save in use UV solidify after this step of baking, introduce highly effective reaction type light trigger and can realize fast setting, favorable solubility before solidifying, forms macromolecular complex mass-energy after solidifying and has good solvent resistance and good temperature tolerance.
Embodiment
embodiment 1
(1) in three mouthfuls of reactors with agitating heater, add 109gPMDA, 183g2,2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa in 200gNMP, normal-temperature reaction 12-24 hour, synthesizing polyamides acid solution; Be warmed up to 150 ℃ of reactions and carry out cyclodehydration imidization in 3-8 hour, obtain the fluorinated polyimide with activity hydroxy, add 105g methacrylic chloride at 10 ℃ of acylation reaction 12-24 hour, obtain active photo-sensistive polyimide oligopolymer.
(2) in three mouthfuls of reactors of stirring are housed, add 98.1g maleic anhydride, add 60g toluene and 12g dimethyl formamide mixed solvent, finally add 0.2g MEHQ.53 ℃ of-65 ℃ of left and right stirring and dissolving 30 minutes, take 107g para-totuidine and slowly drip with dropping funnel, 3-5h drips off, and continues afterwards stirring reaction 0.5h, adds 0.2 copper sulfate and 0.5g tosic acid, is warming up to 150 ℃ and allows its backflow.Observe and occur without the globule, can stop refluxing, return time is generally 2-6h left and right.Be cooled to 60 ℃, adding massfraction is 6% NaCO
3static layering, upper strata is toluene solution, lower floor is the aqueous solution.Upper solution being poured in the beaker that cold water is housed,, there is yellow needle crystal in predominate stirring on one side, then carries out suction filtration, washing, dry, obtains N-to methylbenzene maleimide.
(3) in the active photo-sensistive polyimide oligopolymer of 100g obtained above, add 2.5gN-to methylbenzene maleimide, 7g NVP, 3g Hexafluorobutyl mathacrylate, 0.5g alkylphenol, after mixing in high-speed stirring, shading sealing is preserved.This sample viscosity is 5420 mPa.s, and 350 ℃ of thermal weight losses are 3%, when coat-thickness is 10 μ m, in intensity of illumination, is 3KW(75%) 3 seconds curable, be applicable to outer optical fiber coatings, the at room temperature shading of this sample preserve 3 months substantially unchanged.
embodiment 2
(1) in three mouthfuls of reactors with agitating heater, add 147g BPDA, 183g2,2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa in 220gDMF, normal-temperature reaction 12-24 hour, synthesizing polyamides acid solution; Be warmed up to 150 ℃ of reactions and carry out cyclodehydration imidization in 3-8 hour, obtain the fluorinated polyimide with activity hydroxy, add 105g methacrylic chloride at 10 ℃ of acylation reaction 12-24 hour, obtain active photo-sensistive polyimide oligopolymer.
(2) in three mouthfuls of reactors of stirring are housed, add 98.1g maleic anhydride, add 80g toluene and 15g dimethyl formamide mixed solvent, finally add 0.2g MEHQ.53 ℃ of-65 ℃ of left and right stirring and dissolving 30 minutes, take 115g ethylbenzene amine is slowly dripped with dropping funnel, 3-5h drips off, and continues afterwards stirring reaction 0.5h, adds 0.2 copper sulfate and 0.5g tosic acid, is warming up to 150 ℃ and allows its backflow.Observe and occur without the globule, can stop refluxing, return time is generally 2-6h left and right.Be cooled to 60 ℃, adding massfraction is 6% NaCO
3static layering, upper strata is toluene solution, lower floor is the aqueous solution.Upper solution being poured in the beaker that cold water is housed,, there is yellow needle crystal in predominate stirring on one side, then carries out suction filtration, washing, dry, obtains N-to methylbenzene maleimide.
(3) in the active photo-sensistive polyimide oligopolymer of 100g obtained above, add 2.5gN-to methylbenzene maleimide, 10g tri-contracting four propylene glycol double methacrylates (TPGDA), 5g bis-contracting propylene glycol double methacrylates (TPGDA), 0.5g alkylphenol, after mixing in high-speed stirring, shading sealing is preserved.This sample viscosity is 6820 mPa.s, and 350 ℃ of thermal weight losses are 2%, when coat-thickness is 10 μ m, in intensity of illumination, is 3KW(75%) 15 seconds curable, be applicable to outer optical fiber coatings, the at room temperature shading of this sample preserve 3 months substantially unchanged.
embodiment 3
(1) in three mouthfuls of reactors with agitating heater, add 120gPMDA, 117g2,2-two (amino-4 aminomethyl phenyls of 3-)-HFC-236fa in 210gNMP, normal-temperature reaction 12-24 hour, synthesizing polyamides acid solution; Be warmed up to 150 ℃ of reactions and carry out cyclodehydration imidization in 3-8 hour, obtain the fluorinated polyimide with activity hydroxy, add 105g methacrylic chloride at 10 ℃ of acylation reaction 12-24 hour, obtain active light-sensitive polyimide oligopolymer.
(2) in three mouthfuls of reactors of stirring are housed, add 98.1g maleic anhydride, add 80g toluene and 15g dimethyl formamide mixed solvent, finally add 0.2g MEHQ.53 ℃ of-65 ℃ of left and right stirring and dissolving 30 minutes, take 107g para-totuidine and slowly drip with dropping funnel, 3-5h drips off, and continues afterwards stirring reaction 0.5h, adds 0.2 copper sulfate and 0.5g tosic acid, is warming up to 150 ℃ and allows its backflow.Observe and occur without the globule, can stop refluxing, return time is generally 2-6h left and right.Be cooled to 60 ℃, adding massfraction is 6% NaCO
3static layering, upper strata is toluene solution, lower floor is the aqueous solution.Upper solution being poured in the beaker that cold water is housed,, there is yellow needle crystal in predominate stirring on one side, then carries out suction filtration, washing, dry, obtains N-to methylbenzene maleimide.
(3) in the active light-sensitive polyimide oligopolymer of 100g obtained above, add 2.5gN-to methylbenzene maleimide, 10g NVP, 5g1,6-hexylene glycol double methacrylate (HDDA), 0.5g alkylphenol, after mixing in high-speed stirring, shading sealing is preserved.This sample viscosity is 5870 mPa.s, and 350 ℃ of thermal weight losses are 3%, when coat-thickness is 10 μ m, in intensity of illumination, is 3KW(75%) 5 seconds curable, be applicable to outer optical fiber coatings, the at room temperature shading of this sample preserve 3 months substantially unchanged.
embodiment 4
(1) in three mouthfuls of reactors with agitating heater, add 147g BPDA, 183g2,2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa in 220gNMP, normal-temperature reaction 12-24 hour, synthesizing polyamides acid solution; Be warmed up to 150 ℃ of reactions and carry out cyclodehydration imidization in 3-8 hour, obtain the fluorinated polyimide with activity hydroxy, add 105g methacrylic chloride at 10 ℃ of acylation reaction 12-24 hour, obtain active light-sensitive polyimide oligopolymer.
(2) in three mouthfuls of reactors of stirring are housed, add 98.1g maleic anhydride, add 60g toluene and 12g dimethyl formamide mixed solvent, finally add 0.2g MEHQ.53 ℃ of-65 ℃ of left and right stirring and dissolving 30 minutes, take 107g para-totuidine and slowly drip with dropping funnel, 3-5h drips off, and continues afterwards stirring reaction 0.5h, adds 0.2 copper sulfate and 0.5g tosic acid, is warming up to 150 ℃ and allows its backflow.Observe and occur without the globule, can stop refluxing, return time is generally 2-6h left and right.Be cooled to 60 ℃, adding massfraction is 6% NaCO
3static layering, upper strata is toluene solution, lower floor is the aqueous solution.Upper solution being poured in the beaker that cold water is housed,, there is yellow needle crystal in predominate stirring on one side, then carries out suction filtration, washing, dry, obtains N-to methylbenzene maleimide.
(3) in the active light-sensitive polyimide oligopolymer of 100g obtained above, add 3gN-to methylbenzene maleimide, 7g NVP, 3g Hexafluorobutyl mathacrylate, 0.5g alkylphenol, after mixing in high-speed stirring, shading sealing is preserved.This sample viscosity is 6230 mPa.s, and 350 ℃ of thermal weight losses are 3%, when coat-thickness is 10 μ m, in intensity of illumination, is 3KW(75%) 15 seconds curable, be applicable to outer optical fiber coatings, the at room temperature shading of this sample preserve 3 months substantially unchanged.
Claims (7)
1. a Quick-curing polyimide coating for high-temperature-resistant optical fiber, comprise active light-sensitive polyimide oligopolymer, response type light trigger, reactive thinner, thermo-stabilizer, the weight percent that each amounts of components accounts for coating total amount is active light-sensitive polyimide oligopolymer 25～75%, reactive thinner 5～70%, response type light trigger 0.1～15%, thermo-stabilizer 0.1～10%, wherein said active light-sensitive polyimide oligopolymer is 2 of 10-35% by choosing mass percent, 2-two (amino-4 hydroxy phenyls of 3-)-HFC-236fa, 2, 2-two (amino-4 aminomethyl phenyls of 3-)-HFC-236fa, 2, 2-is two, and (4-is amino, phenyl) pyromellitic acid anhydride of any one in HFC-236fa and 10-30% or bibenzene tetracarboxylic dianhydride first synthesizing polyamides acid in the solvent of 25-75%, the imidization of dewatering again, finally add the methacrylic chloride of 5-10% to be prepared from.
2. Quick-curing polyimide coating for high-temperature-resistant optical fiber according to claim 1, wherein said solvent is dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
3. Quick-curing polyimide coating for high-temperature-resistant optical fiber according to claim 1, wherein said response type light trigger is that N-is to methylbenzene maleimide.
4. Quick-curing polyimide coating for high-temperature-resistant optical fiber according to claim 1, wherein said reactive thinner is vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, vinylbenzene, three contracting four propylene glycol double methacrylates, two contracting propylene glycol double methacrylates, NVP, 1, one or more in 6-hexylene glycol double methacrylate.
5. according to the Quick-curing polyimide coating for high-temperature-resistant optical fiber described in claim 1, wherein said thermo-stabilizer is thiobisphenol, alkylidene bisphenols, alkylphenol, xenol compound, phosphite, phosphoric acid salt, one or more in organic amine.
6. according to the Quick-curing polyimide coating for high-temperature-resistant optical fiber described in any one in claim 1～5, as inner layer optical fiber paint, outer optical fiber coatings, special optical fiber coating, aerospace, with heatproof radiation resistant optical fiber coating, use.
7. according to the preparation method of the Quick-curing polyimide coating for high-temperature-resistant optical fiber described in any one in claim 1～5, wherein described active light-sensitive polyimide oligopolymer, response type light trigger, reactive thinner, thermo-stabilizer high-speed stirring are mixed, sealing shading is preserved.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9983376B2 (en) | 2015-04-23 | 2018-05-29 | Corning Optical Communications LLC | High-data-rate electrical interconnect cables |
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| CN102816517B (en) * | 2012-08-23 | 2014-11-05 | 东华大学 | Light cured polyimide coating for optical fiber, and preparation method thereof |
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| CN104927072B (en) * | 2015-05-29 | 2019-05-14 | 六安市杜尔邦绝缘材料有限公司 | A kind of Kapton and preparation method thereof of solvent resistant low thermal coefficient of expansion |
| CN105837760B (en) * | 2016-05-19 | 2018-08-07 | 潘盈 | A kind of 3D printing polyimide light-sensitive material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263524A (en) * | 1997-05-27 | 2000-08-16 | 第一化学公司 | Aromatic maleimides and their use as photoinitiators |
| CN1468907A (en) * | 2002-07-17 | 2004-01-21 | �ն��繤��ʽ���� | Photosensitive polyimide resin precursor composition, optical polyimide, light wave guide tube and process for producing the same light wave guide tube |
| CN101014643A (en) * | 2005-01-28 | 2007-08-08 | 索尼化学&信息部件株式会社 | Polyimide compound and flexible wiring board |
| CN101265328A (en) * | 2008-04-23 | 2008-09-17 | 东华大学 | Method for preparing negative photosensitive polyimide based on 2,2-di[4-(2,4-diaminophenyloxy)phenyl]hexafluoropropane |
| CN101921403A (en) * | 2010-09-21 | 2010-12-22 | 北京市射线应用研究中心 | Synthesizing method of polyimide material |
-
2011
- 2011-12-05 CN CN201110397303.8A patent/CN102492320B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263524A (en) * | 1997-05-27 | 2000-08-16 | 第一化学公司 | Aromatic maleimides and their use as photoinitiators |
| CN1468907A (en) * | 2002-07-17 | 2004-01-21 | �ն��繤��ʽ���� | Photosensitive polyimide resin precursor composition, optical polyimide, light wave guide tube and process for producing the same light wave guide tube |
| CN101014643A (en) * | 2005-01-28 | 2007-08-08 | 索尼化学&信息部件株式会社 | Polyimide compound and flexible wiring board |
| CN101265328A (en) * | 2008-04-23 | 2008-09-17 | 东华大学 | Method for preparing negative photosensitive polyimide based on 2,2-di[4-(2,4-diaminophenyloxy)phenyl]hexafluoropropane |
| CN101921403A (en) * | 2010-09-21 | 2010-12-22 | 北京市射线应用研究中心 | Synthesizing method of polyimide material |
Non-Patent Citations (1)
| Title |
|---|
| 孙自淑.均聚型光敏聚酰亚胺的合成与性能研究.《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》.2006,(第10期), * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9983376B2 (en) | 2015-04-23 | 2018-05-29 | Corning Optical Communications LLC | High-data-rate electrical interconnect cables |
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