CN102161801B - Ultraviolet light deeply crosslinked ethylene-propylene-diene mischpolymere rubber cable material and preparation method of insulation or protective sleeve layer thereof - Google Patents
Ultraviolet light deeply crosslinked ethylene-propylene-diene mischpolymere rubber cable material and preparation method of insulation or protective sleeve layer thereof Download PDFInfo
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Abstract
The invention relates to an ultraviolet light deeply crosslinked ethylene-propylene-diene mischpolymere rubber cable material and a preparation method of an insulation and protective sleeve layer thereof. The invention is characterized in that: ethylene-propylene-diene mischpolymere rubber and grafting modified ethylene-propylene-diene mischpolymere rubber are used as a base stock, an inorganic filler, a photoinitiation system consisting of a cation photoinitiator and a radical photoinitiator and the like are added, and the cable material is made by blending and extrusion; and a coated cable insulation or protective sleeve layer is subjected to molten online continuous ultraviolet light radiation in an ultraviolet radiation crosslinking equipment which is provided with a thermoelectron excited medium voltage mercury arc lamp or an H-type, D-type or V-type microwave-excited electrodeless lamp as a special light source to obtain a deeply and uniformly crosslinked ethylene-propylene-diene mischpolymere rubber cable insulation or protective sleeve layer. The cable material and the preparation technique have the advantages that: the needed crosslinking equipment is low in investment; the process is simple; the operation and maintenance are convenient; the production efficiency is high; the product cost is low and product quality is high; and energy conservation and environment protection are realized. Thus, the cable material and the preparation technique can be widely used for manufacturing high-performance special crosslinked rubber wire and cable products and the like.
Description
Technical field
The invention belongs to the rubber cross field of cables, particularly the preparation method of the insulation of ultraviolet deep-crosslinked EPT rubber cable or sheath material and insulation thereof or restrictive coating.
Background technology
Terpolymer EP rubber (EPDM) is widely used as wire cable insulating or sheath material because having the characteristics such as electrical property excellence, heat-resisting ageing-resisting excellent property, low temperature flexibility be good, particularly mine cable and shipboard cable and other special cable.Traditional terpolymer EP rubber wire cable insulating or the cross-linking method of restrictive coating mainly contain superoxide chemical crosslink technique, high-energy radiation crosslinking and silane cross-linking method.European patent EP 1453866 discloses the material system that forms with EPDM, calcined kaolin, Low Density Polyethylene, silane coupling agent and paraffin and prepared crosslinked terpolymer EP rubber flexible cable under the chemically crosslinked condition of dicumyl peroxide thermal initiation, the tensile strength of goods is greater than 8.2MPa, and elongation at break is higher than 250%.US Patent No. 2004242781 discloses with employing chemical crosslink techniques such as EPDM, kaolin, organo-peroxide, zinc oxide, paraffin oil and oxidation inhibitor and has prepared EPT rubber cable, and the tensile strength of goods is greater than 9MPa, and elongation at break is higher than 200%.The composite system that China Patent Publication No. CN1783356 discloses EPDM, calcinated argil, anti-aging agent, organo-peroxide, coupling agent and paraffin adopts pressure terpolymer EP rubber insulated cable in the chemical crosslink technique preparation, product tensile strength is greater than 6MPa, and elongation at break is higher than 300%.China's " elastomerics " magazine (2006 the 5th phase the 51st page) has been described with employing chemical crosslink techniques such as EPDM, calcium carbonate, kaolin, talcum powder, dicumyl peroxide, tenderizer and anti-aging agent and has been prepared EPT rubber cable, the tensile strength of goods is greater than 5MPa, and elongation at break is higher than 350%.Chinese Magazines " New Chemical Materials " (2006 the 1st phase of the 34th volume the 57th page) has been reported with nano silicon, nano-calcium carbonate as reinforced filling, and adopt the high-energy radiation crosslinking to prepare ethylene propylene diene monomer (EPDM) material, the tensile strength maximum of resulting product can reach 12MPa, and elongation at break is greater than 400%." radiation physics chemistry " (Radiation Physics Chemistry, 1983,22 (3-5), 564-74) described a kind of rubber insulation material that is comprised of EPDM rubber, ethylene vinyl acetate copolymer and the oxidation inhibitor of high ethylene content through electron beam to irradiate crosslinked, aging resistance and the electrical property of goods are good.China Patent Publication No. CN1058507C discloses with employing irradiation crosslinkings such as terpolymer EP rubber, Low Density Polyethylene, light calcium carbonate, decabromodiphynly oxide, molybdenum oxide, cross-linking radiation agent and has prepared crosslinked mine rubber flexible cable, the temperature resistant grade of goods is high, machinery, excellent electrical properties.Disclose with ethylene-propylene rubber(EPR) in the Chinese patent application numbers 200910172429, the method of the employing crosslinked with silicane such as composite silane, catalyzer, lubricant prepares coupling ethylene propylene rubber cable material, this CABLE MATERIALS can be in 90 ℃ of water fast speed crosslinked, and heat extends≤80%.Yet, to prepare the deficiency that EPT rubber cable exists be that its production efficiency is low, technical process is complicated to the superoxide chemical crosslink technique in above-mentioned the whole bag of tricks, need to carry out the crosslinked of long period by tens meters long high-pressure and high-temperature steam curing tube, power consumption is large, the efficiency utilization ratio is very low, and the effective rate of utilization of its heat energy only is about 10% etc.; The facility investment of high-energy radiation crosslinking is higher, the comparatively complicated and protection condition harshness of Operation and Maintenance, and the electric wire that is only suitable for doing less wire diameter owing to its process characteristic is not suitable for doing the cable of larger wire diameter; And silane cross-linking method relates to hydrolysis reaction, the poor stability of goods, and the pressure high-temp resistant grade is also lower.
The in recent years photo-crosslinking research work of relevant pure EPDM rubber also early has report, U.S.'s " rubber chemistry and technology " magazine (Rubber Chemistry and Technology for example, 592:62,1989) described with crack type photoinitiator benzoin dimethylether and multi-group crosslink agent's orthoformic acid triacrylate as the light initiation system of EPDM rubber, utilized high voltage mercury lamp can make the thick pure EPDM glue-line of 10mm reach photo-crosslinking.Yet, the photo-crosslinking of EPDM fails to achieve success in the cable industry application always, its major cause is that the EPDM rubber as cable application all needs to add the reinforcement inorganic fillings that accounts for the 50-60% weight ratio usually, and the EPDM rubber that contains high amount of inorganic filler is difficult to make UV-light to pass and occur crosslinked.
The applicant discloses the EPDM rubber that adopts Inorganic Fillers Filled and has carried out ultraviolet light cross-linking prepare crosslinked EPDM cable insulation and sheath material under the light initiation system of free radical photo-initiation and linking agent in Chinese patent application numbers 200810244782, the tensile strength of resulting product is greater than 6.5MPa, elongation at break is greater than 300%, and volume specific resistance is higher than 10
13Ω cm.Simultaneously in Chinese patent application numbers 200910116279, the applicant discloses again EPDM rubber take metal hydroxides as main flame retardant and has carried out ultraviolet light cross-linking prepare cross-linking flame-retardant EPDM cable insulation and sheath material under the light initiation system of free radical photo-initiation and linking agent.Yet in the actual use procedure of above-mentioned two patent applications, find no matter to have added inorganic filler or the metal hydroxide combustion inhibitor of reinforcement, except they are deteriorated the mechanical property and processing characteristics of polymeric matrix, what cause larger negative impact is seriously to have hindered the penetrativity of UV-light in polymer materials, it is full cross-linked to cause the bottom of thicker sample (for example 1.5mm and above thickness) to obtain, and has had a strong impact on use properties and the range of application of material.Therefore, how to overcome and added the above-mentioned shortcoming that high amount of inorganic filler or fire retardant bring, improve penetration depth and the photo-initiated crosslinking efficient key technical problem that become development the type photo-crosslinking EPDM cable material of UV-light in these rubber/inorganic filler matrix material.
The polymkeric substance ultraviolet light cross-linking at present the most normally used class is free radical photo-initiation, such as hydrogen-capture-type light initiator benzophenone (BP) class and crack type photoinitiator benzoin dimethylether (BDK) etc., they produce free radical and cause crosslinking reaction behind absorbing ultraviolet light, but since the penetration power of UV-light a little less than, especially in containing the thicker sample of high amount of inorganic filler, be difficult to be penetrated into the deep layer initiation radical crosslinking reaction of material, cause the reduction of photo-initiated crosslinking efficient and greatly limited requiring than the application in heavy insulation or the restrictive coating cable.Another kind of very important light trigger is cation light initiator, and a small amount of application is only arranged in the coating curing field at present.
Summary of the invention
The object of the invention is to overcome deficiency and the shortcoming that above-mentioned prior art medium ultraviolet photo-crosslinking terpolymer EP rubber exists.Find that novel light initiation system that cation light initiator and free radical photo-initiation combine is at light intensity 400-4000mW/cm through the contriver is surprised in the development research of long-term electric wire and production practice
2Carry out the unusual effect that melting attitude on-line continuous ultraviolet light irradiation obtains deep-crosslinked under the specific UV light source condition that wavelength 200-500nm and intensity of emission spectra distribution thereof and cation light initiator absorption spectrum and intensity distribution thereof are complementary, be used simultaneously the complex art means such as graft modification terpolymer EP rubber solve UV-light in the terpolymer EP rubber of large addition mineral filler reinforcement the deep layer penetrativity and cause the art problem of the crucial skill such as serious deteriorated of the mechanics of materials and processing characteristics, in order to provide a kind of facility investment low, technique is simple, production efficiency is high, the product cost lower performance is good, energy-conserving and environment-protective, can reach the preparation method of ultraviolet deep-crosslinked EPT rubber cable insulation or sheath material (general designation CABLE MATERIALS) and insulation or the restrictive coating of the even ultraviolet light cross-linking terpolymer EP rubber of degree of depth electric wire novel material and new technology.
Ultraviolet deep-crosslinked EPT rubber cable insulation provided by the invention or sheath material, it is characterized in that with terpolymer EP rubber and graft modification terpolymer EP rubber (any ratio) as base-material, by 100 parts of base-material gross weights, add mineral filler 100-180 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.5-5.0 weight part, multi-group crosslink agent 0.5-5.0 weight part, composite antioxidant 0.01-1.0 weight part, tenderizer 5.0-10.0 weight part, silane coupling agent 0.5-5.0 weight part
Ultraviolet deep-crosslinked EPT rubber cable insulation provided by the invention or sheath material prepare the method for cable insulation or restrictive coating, it is characterized in that with terpolymer EP rubber and graft modification terpolymer EP rubber (any ratio) as base-material, by 100 parts of base-material gross weights, add mineral filler 100-180 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.5-5.0 weight part, multi-group crosslink agent 0.5-5.0 weight part, composite antioxidant 0.01-1.0 weight part, tenderizer 5.0-10.0 weight part, after silane coupling agent 0.5-5.0 weight part mixes, at 100-150 ℃ of mixing 8-10 minute, extrude through twin screw extruder again and make photo-crosslinking EPT rubber cable material; Then melt extrude this EPT rubber cable material of coating at conductive cable cores and become insulation layer or restrictive coating, immediately at light intensity 400-4000mW/cm
2, wavelength 200-500nm and light distribution thereof and above-mentioned cationic photopolymerization initiator system be complementary, can adopt respectively and be equipped with that thermoelectron excites middle pressure mercuryarc lamp or the V-type microwave-excitation Non-polarized lamp that is equipped with the H type, is added with the D type of ferro element or is added with gallium element is in the ultraviolet light irradiation cross-linking apparatus of specific light source insulation layer or restrictive coating to be carried out melting attitude on-line continuous ultraviolet light irradiation 0.5-20 second, evenly be cross-linked into EPT rubber cable insulation layer or restrictive coating to reach the degree of depth.
Ultraviolet deep-crosslinked EPT rubber cable insulation provided by the invention and sheath material and prepare cable insulation or the method for restrictive coating in, described terpolymer EP rubber includes the H type terpolymer EP rubber that E type terpolymer EP rubber that the 3rd monomer is the vinylidene norbornylene, D type terpolymer EP rubber that the 3rd monomer is dicyclopentadiene or the 3rd monomer are Isosorbide-5-Nitrae-hexadiene.
Described graft modification terpolymer EP rubber is glycidyl methacrylate graft terpolymer EP rubber, maleic anhydride graft terpolymer EP rubber or n-butyl acrylate grafting terpolymer EP rubber.
Described mineral filler is white carbon black, potter's clay or calcinated argil, talcum powder, calcium carbonate, magnesiumcarbonate, aluminum oxide or its mixture (any ratio).
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt (also claiming the iron arene salt), for example phosphofluoric acid triaryl sulfonium salts, ferrocene-four-fluoroborate, cationic photoinitiator, triphenyl hexafluoro-antimonic acid sulfosalt or two dodecylbenzene hexafluoroarsenate salt compounded of iodine.The effect characteristics of cation light initiator are to cause crosslinking reaction through the cation activity center that ultraviolet light irradiation is activated generation, and the crosslinked of positively charged ion initiation generally is not subjected to sample to stop the impact of illumination or thickness of sample, because cationoid reaction has produced new cation activity center at polymer chain again when chain shifts termination reaction, can in stopping the polymeric matrix deep layer position that ultraviolet lighting or UV-light can't arrive, continue to cause the crosslinking reaction that strengthens, that is to say, the positively charged ion photo-initiated crosslinking is not dead crosslinking reaction, as long as the initial stage is accepted photoirradiation, the later stage, dark crosslinking reaction was carried out in the same old way smoothly.Cation light initiator diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, main absorption spectrum concentrates on usually less than 300nm wave band district, and the main absorption spectrum of ferrocene salt (also claiming iron arene salt) cationoid light trigger is then usually greater than 360nm wave band district.But the emmission spectrum scope of present normally used medium pressure mercury lamp and the main absorption spectrum of intensity distribution and these cation light initiators and intensity distribution Incomplete matching, thereby can't give full play to its photo-initiated crosslinking efficient.The present invention adopts following two kinds of technical schemes to solve this " Incomplete matching " problem: the light initiation system that one adopts cation light initiator to match with free radical photo-initiation, such as a kind of effective sensitizing agent of normally used free radical photo-initiation benzophenone (also claiming the transfer transport activator), the existence of free radical photo-initiation can improve the photo-initiated crosslinking efficient of cation light initiator under ultraviolet light irradiation; Its two ultraviolet source of selecting suitable emission wavelength ranges and intensity distribution thereof is complementary with absorbing wavelength and the intensity distribution thereof of corresponding cation light initiator, the cation light initiator that absorbing wavelength is concentrated on less than 300nm just can adopt H type microwave-excitation Non-polarized lamp, because its main absorption peak concentrates between the 200-300nm, the cation light initiator that absorbing wavelength is concentrated on greater than 360nm then can adopt respectively microwave-excitation D type or the V-type lamp that has added metallic elements of ferrum or gallium.Add ferro element in the mercury lamp ultraviolet ray intensity of 320-400nm place output is obviously increased, then can make the very high ultraviolet light intensity of 405-440nm place output when adding gallium element.
Described free radical photo-initiation can select the interior cracking type of molecule or/and intermolecular hydrogen-capture-type light initiator; Wherein crack type photoinitiator can be selected benzoin dimethylether Irgacure 651 (BDK), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone Irgacure 907(I-907), Alpha-hydroxy phenyl isopropyl ketone Darocur 1173(D-1173), acyl group phosphorous oxides photoinitiator Irgacure 1700(I-1700), dialkoxy methyl phenyl ketone Irgacure 2959(I-2959), 1-hydroxyl-cyclohexyl-phenyl ketone Irgacure 184(I-184) or 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone Irgacure 369(I-369); Described hydrogen-capture-type light initiator can be selected benzophenone (BP), 2-chlorobenzophenone (2-CBP), 4-chlorobenzophenone (4-CBP), 4,4-dichloro benzophenone (4,4 '-DCBP), dodecyl benzophenone, Oxoxanthone, anthraquinone or Fluorenone; Above-mentioned light trigger can use separately, also can two kinds same kind light trigger or two kinds of dissimilar light triggers compound (any ratio) use, better with the effect that adopts compound free radical photo-initiation.
Described multi-group crosslink agent is selected from triallyl cyanurate (TAC), cyamelide triallyl (TAIC), hydroxymethyl-propane three (methyl) acrylate (TMPTA), trimethylolpropane tris allyl ether (TMPAE), tetramethylolmethane three allyl ethers (PETAE), tetramethylolmethane tetraene propyl ether or triethylene glycol dimethacrylate (TEGMA), or its mixture.
Described composite antioxidant is selected from phenols, phosphorous acid esters, phosphoric acid ester or contains the composite antioxidant of thioesters kind antioxidant (any ratio); Wherein phenolic antioxidant comprises 2, the 6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol (oxidation inhibitor 246), 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) (antioxidant 300 #) or four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010); Described phosphorous acid esters or phosphoric acid ester oxidation inhibitor comprise triphenyl phosphite (TPP), tricresyl phosphite (2,4-di-tert-butyl phenyl) ester (irgasfos 168), the different monooctyl ester of tricresyl phosphite (TIOP) or tricresyl phosphate benzene methyl; The described thioesters kind antioxidant that contains comprises Tyox B (DLTP), thio-2 acid bay octadecyl ester (LSTP) or thio-2 acid two (13) ester (DTDTP); Preferably with phenolic antioxidant and phosphorous acid esters or contain the composite composite antioxidant of thioesters kind antioxidant, more preferably [3-(3 ' with four, 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and triphenyl phosphite (TPP) or tricresyl phosphite (2,4-di-tert-butyl phenyl) ester (irgasfos 168) or the composite composite antioxidant of Tyox B (DLTP).
Described tenderizer is selected from low molecular weight polyethylene, aromatic hydrocarbon oil, naphthenic oil, paraffin oil or microcrystalline wax.
Described silane coupling agent is selected from γ-methacryloxypropyl trimethoxy silane (KH570), vinyltriethoxysilane (SG-Si-151), γ-aminopropyl triethoxysilane (KH550), γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), gamma-mercaptopropyltriethoxysilane (KH580) and/or two-(the silica-based propyl group of γ-triethoxy) tetrasulfide (RSi-E).
Described specific UV light source is the two large class medium pressure mercury lamps that thermoelectron excites middle pressure mercuryarc lamp and microwave-excitation Non-polarized lamp, and wherein the microwave-excitation Non-polarized lamp includes H type lamp, is added with the D type lamp of ferro element and is added with the V-type lamp of gallium element.As described in the above cation light initiator, can change emmission spectrum and the intensity distribution scope thereof of ultraviolet lamp by adding metallic elements of ferrum or gallium, in order to cooperate absorption spectrum and the intensity distribution scope thereof of cation light initiator, can make cation light initiator absorb more UV-light energy during illumination, strengthen the crosslinked ability of its deep layer and improve photo-initiated crosslinking efficient.Ultraviolet deep provided by the invention { layer } insulation of crosslinked EPT rubber cable and the preparation method of sheath material and insulation layer or restrictive coating, be characterized in the light initiation system that adopts cation light initiator to match with free radical photo-initiation, this light initiation system can greatly improve the deep layer penetrativity of UV-light under the ultraviolet light irradiation condition with suitable emmission spectrum and intensity distribution scope thereof cooperates, strengthen photo-initiated crosslinking efficient, its quality product high-performance is good, is a kind of production method of ultraviolet deep-crosslinked terpolymer EP rubber electric wire and cable material of novelty.
Compare with the crosslinking technological of present existing EPT rubber cable, the preparation method of ultraviolet deep-crosslinked EPT rubber cable material provided by the invention and insulation layer or restrictive coating has following distinguishing feature:
1, the novel light initiation system that the present invention has adopted cation light initiator and free radical photo-initiation to combine, except the free radical photo-initiated crosslinking, also can further finish crosslinking reaction by the cation activity center that the cation light initiator in the system causes, and this cationic crosslinked reaction generally is not subjected to the impact of thickness of sample, because cationoid reaction has produced again new cation activity center on polymer chain when chain shifts termination reaction, can in stopping the polymeric matrix deep layer position that ultraviolet lighting or UV-light can't arrive, continue to cause the crosslinking reaction (also claiming dark reaction) that strengthens.Meanwhile, the free radical photo-initiation that uses in the system is the effective sensitizing agent of cation light initiator (also claiming the transfer transport activator) normally, and the UV-light that can further strengthen cation light initiator causes cross-linking efficiency.So just overcome that the simple free radical photo-initiation that uses must could produce the shortcoming of crosslinking reaction behind the absorbing ultraviolet light in the former Chinese patent application numbers 200810244782 and 200910116279, thereby efficiently solved the difficult problem that the UV-light penetration power is difficult to be penetrated into the terpolymer EP rubber matrix deep layer initiation crosslinking reaction that contains high amount of inorganic filler a little less than.
2, the present invention has selected light intensity 400-4000mW/cm
2The specific UV light source that employed cationic photopolymerization initiator system absorption spectrum and intensity distribution thereof are complementary in wavelength 200-500nm and intensity distribution thereof and the material prescription, solve the main absorption spectrum of the emmission spectrum scope of present normally used medium pressure mercury lamp and intensity distribution and cation light initiator and intensity distribution Incomplete matching and caused to give full play to the problem of its photo-initiated crosslinking efficient, can make the cationic photopolymerization initiator system absorb more UV-light energy, greatly improved the deep layer penetrativity of UV-light in containing the terpolymer EP rubber of high amount of inorganic filler, at utmost improved the efficient of cationic photopolymerization initiator system photo-initiated crosslinking, thereby the uniform light cross-linking depth of this ethylene propylene diene monomer (EPDM) material is brought up to more than the 3.0mm from original not enough 1.5mm.
3, graft modification terpolymer EP rubber and silane coupling agent have been adopted simultaneously in the material prescription of the present invention, greatly improve consistency and the dispersiveness of mineral filler in terpolymer EP rubber, obviously improved mechanical property, electric property, heat aging performance and the processing characteristics of photo-crosslinking ethylene propylene diene monomer (EPDM) material.
4,, chemically crosslinked crosslinked with existing traditional high-energy radiation compared with the crosslinked with silicane technology, the preparation method of ultraviolet deep-crosslinked EPT rubber cable material of the present invention and insulation and restrictive coating has unique technical superiority: the investment of required cross-linking apparatus is low, technique simple, convenient operating maintenance, and production efficiency is high, good, the energy-conservation again environmental protection of product cost inferior quality.
Embodiment
The present invention does further concrete detailed explanation with the following example and comparative example to the present invention, but protection domain of the present invention is not limited to the following example.
Embodiment 1
In Banbury mixer, drop into 80 parts of E type EPDM by weight, 10 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 40 parts of calcinated argils, 60 parts of talcum powder, 3.5 parts of phosphofluoric acid triaryl sulfonium salts, 1.0 parts of BDK, 1.5 parts of TMPTA, 0.3 part of antioxidant 1010,0.1 part of DLTP, 3 parts of paraffin oils, 0.8 part of silane coupling agent KH570,100-150 ℃ of mixing 8-10 minute evenly after, extrude through twin screw extruder again and make photo-crosslinking EPT rubber cable material; Then melt extrude the insulation layer that is overmolding to 3.0mm or restrictive coating, insulation layer or restrictive coating are carried out the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take H type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source immediately at conductive cable cores, crosslinking time is 8 seconds.The tensile strength of the ultraviolet deep-crosslinked EPT rubber cable material of present embodiment preparation is 8.3MPa, elongation at break 390%, and hot unit elongation 45%, volume specific resistance are 2.1 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Comparative example 1
Do not adopt cation light initiator phosphofluoric acid triaryl sulfonium salts but keep simultaneous test in light trigger parts by weight and the constant situation of other conditions: in Banbury mixer, drop into 80 parts of E type EPDM by weight, 10 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 40 parts of calcinated argils, 60 parts of talcum powder, 4.5 parts of BDK, 1.5 parts of TMPTA, 0.3 part of antioxidant 1010,0.1 part of DLTP, 3 parts of paraffin oils, 0.8 part of silane coupling agent KH570,100-150 ℃ of mixing 8-10 minute evenly after, extrude through twin screw extruder again and make photo-crosslinking EPT rubber cable material; Then melt extrude the insulation layer that is overmolding to 3.0mm or restrictive coating, insulation layer or restrictive coating are carried out the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take H type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source immediately at conductive cable cores, crosslinking time is 8 seconds.The tensile strength of the ultraviolet light crosslinked EPT rubber cable material of this comparative example preparation is 6.2MPa, elongation at break 480%, and hot elongation test can't be passed through, and volume specific resistance is 1.1 * 10
12Ω .m can't be by the thermal ageing test of 135 ℃ * 168h.
Embodiment 2
In Banbury mixer, drop into 85 parts of E type EPDM by weight, 5 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 60 parts of talcum powder, 60 parts of nano-calcium carbonates, 2.0 parts of ferrocene-four-fluoroborate, 2.0 parts of BP, 1.5 parts of TAIC, 0.2 part of antioxidant 1010,0.1 part of DLTP, 5 parts of paraffin oils, 0.8 part of silane coupling agent KH570,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude this CABLE MATERIALS of coating at conductive cable cores and become 2.5mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take V-type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 1.5 seconds.Experimental result shows: the tensile strength of the ultraviolet deep-crosslinked EPT rubber cable material of present embodiment preparation is 12.8MPa, elongation at break 340%, and hot unit elongation 65%, volume specific resistance are 2.5 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Comparative example 2
Adopt common middle pressure mercuryarc lamp and crosslinking time to increase to 15 seconds and contrast experiment in the constant situation of other condition: in Banbury mixer, to drop into 85 parts of E type EPDM by weight, 5 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 60 parts of talcum powder, 60 parts of nano-calcium carbonates, 2.0 parts of ferrocene-four-fluoroborate, 2.0 parts of BP, 1.5 parts of TAIC, 0.2 part of antioxidant 1010,0.1 part of DLTP, 5 parts of paraffin oils, 0.8 part of silane coupling agent KH570,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude this CABLE MATERIALS of coating at conductive cable cores and become 2.5mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take middle pressure mercuryarc lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the ultraviolet light crosslinked EPT rubber cable material of this comparative example preparation is 6.8MPa, elongation at break 500%, and heat is extended experiment and can't be passed through, and volume specific resistance is 1.2 * 10
12Ω .m can't be by the thermal ageing test of 135 ℃ * 168h.
Embodiment 3
In Banbury mixer, drop into 75 parts of H type EPDM by weight, 10 parts of glycidyl methacrylate graft terpolymer EP rubbers, 15 parts of n-butyl acrylate grafting terpolymer EP rubbers, 50 parts of talcum powder, 60 parts of calcinated argils, 2.0 parts of cationic photoinitiators, 1.5 parts of BDK, 3 parts of TAIC, 0.5 part of irgasfos 168,0.4 part of DTDTP, 5 parts of paraffin oils, 1 part of Silane coupling agent KH550,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude this CABLE MATERIALS of coating at conductive cable cores and become 3.2mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take D type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of the ultraviolet deep-crosslinked terpolymer EP rubber of present embodiment preparation is 12.6MPa, elongation at break 360%, and hot unit elongation 50%, volume specific resistance are 4.4 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Comparative example 3
Adopt common middle pressure mercuryarc lamp to substitute D type microwave-excitation Non-polarized lamp and remain unchanged simultaneous test in the situation of crosslinking time and other condition: in Banbury mixer, to drop into 75 parts of H type EPDM by weight, 10 parts of glycidyl methacrylate graft terpolymer EP rubbers, 15 parts of n-butyl acrylate grafting terpolymer EP rubbers, 50 parts of talcum powder, 60 parts of calcinated argils, 2.0 parts of cationic photoinitiators, 1.5 parts of BDK, 3 parts of TAIC, 0.5 part of irgasfos 168,0.4 part of DTDTP, 5 parts of paraffin oils, 1 part of Silane coupling agent KH550,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude this CABLE MATERIALS of coating at conductive cable cores and become 3.2mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take middle pressure mercuryarc lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of the ultraviolet light crosslinked EPT rubber cable material of this comparative example preparation is 7.6MPa, elongation at break 510%, and heat is extended experiment and can't be passed through, and volume specific resistance is 1.4 * 10
12Ω .m can't be by the thermal ageing test of 135 ℃ * 168h.
Embodiment 4
In Banbury mixer, drop into 80 parts of D type EPDM by weight, 15 parts of glycidyl methacrylate graft terpolymer EP rubbers, 5 parts of n-butyl acrylate grafting terpolymer EP rubbers, 60 parts in calcium carbonate, 60 parts in magnesiumcarbonate, 2.0 parts of triphenyl hexafluoro-antimonic acid sulfosalts, 1.5 parts of BDK, 0.5 part of I-184,2.5 parts of TAIC, 0.6 part of antioxidant 1010,0.5 part of TPP, 5 parts of paraffin oils, 1 part of silane coupling agent KH580,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude at conductive cable cores and coat this CABLE MATERIALS and become 1.6mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take common middle pressure mercuryarc lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the ultraviolet deep-crosslinked EPT rubber cable material of present embodiment preparation is 10.3MPa, elongation at break 440%, and hot unit elongation 56%, volume specific resistance are 4.3 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Comparative example 4
Do not adopt cation light initiator triphenyl hexafluoro-antimonic acid sulfosalt but keep simultaneous test in light trigger parts by weight and the constant situation of other conditions: in Banbury mixer, drop into 80 parts of D type EPDM by weight, 15 parts of glycidyl methacrylate graft terpolymer EP rubbers, 5 parts of n-butyl acrylate grafting terpolymer EP rubbers, 60 parts in calcium carbonate, 60 parts in magnesiumcarbonate, 3 parts of BDK, 1.0 parts of I-184,2.5 parts of TAIC, 0.6 part of antioxidant 1010,0.5 part of TPP, 5 parts of paraffin oils, 1 part of silane coupling agent KH580,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude at conductive cable cores and coat this CABLE MATERIALS and become 1.6mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take common middle pressure mercuryarc lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the ultraviolet light crosslinked EPT rubber cable material of this comparative example preparation is 7.3MPa, elongation at break 550%, and heat is extended experiment and can't be passed through, and volume specific resistance is 1.3 * 10
12Ω .m can't be by the thermal ageing test of 135 ℃ * 168h.
Embodiment 5
In Banbury mixer, drop into 80 parts of D type EPDM by weight, 10 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 60 parts in calcium carbonate, 60 parts of calcinated argils, 5 parts of two dodecylbenzene hexafluoroarsenate salt compounded of iodine, 4 parts of dodecyl benzophenone, 3 parts of TAIC, 0.5 part of antioxidant 1010,0.5 part of DTDTP, 5 parts of paraffin oils, 1 part of Silane coupling agent KH550,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS; Then melt extrude at conductive cable cores and coat this CABLE MATERIALS and become 2.5mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take H type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source immediately, crosslinking time is 4 seconds.Experimental result shows: the tensile strength of the ultraviolet deep-crosslinked terpolymer EP rubber of present embodiment preparation is 10.5MPa, elongation at break 380%, and hot unit elongation 50%, volume specific resistance are 3.4 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Embodiment 6
In Banbury mixer, drop into 85 parts of H type EPDM by weight, 5 parts of glycidyl methacrylate graft terpolymer EP rubbers, 10 parts of maleic anhydride graft terpolymer EP rubbers, 40 parts in aluminum oxide, 70 parts of calcinated argils, 2.0 parts of ferrocene-four-fluoroborate, 1.5 parts of BDK, 0.5 part of I-184,2 parts of TMPAE, 0.7 part of antioxidant 1010,0.3 part of TPP, 10 parts of low molecular weight polyethylenes, 1 part of Silane coupling agent KH550,100-150 ℃ mixing evenly after, extrude through twin screw extruder again and make the EPDM CABLE MATERIALS, then melt extrude this CABLE MATERIALS of coating at conductive cable cores and become 1.6mm insulation layer or restrictive coating, insulation layer or restrictive coating are carried out immediately the ultraviolet light irradiation cross-linking of melting attitude on-line continuous in take V-type microwave-excitation Non-polarized lamp as the ultraviolet light irradiation cross-linking apparatus of light source, crosslinking time is 0.5 second.Experimental result shows: the tensile strength of the ultraviolet deep-crosslinked terpolymer EP rubber of present embodiment preparation is 11.2MPa, elongation at break 420%, and hot unit elongation 55%, volume specific resistance are 5.3 * 10
12Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Claims (7)
1. a ultraviolet deep-crosslinked EPT rubber cable insulation or sheath material, it is characterized in that: with terpolymer EP rubber and graft modification terpolymer EP rubber as base-material, by 100 parts of base-material gross weights, add mineral filler 100-180 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.5-5.0 weight part, multi-group crosslink agent 0.5-5.0 weight part, composite antioxidant 0.01-1.0 weight part, tenderizer 5.0-10.0 weight part, silane coupling agent 0.5-5.0 weight part;
Described terpolymer EP rubber is that the 3rd monomer is the H type terpolymer EP rubber that the E type terpolymer EP rubber of vinylidene norbornylene, D type terpolymer EP rubber that the 3rd monomer is dicyclopentadiene or the 3rd monomer are Isosorbide-5-Nitrae-hexadiene;
Described graft modification terpolymer EP rubber is glycidyl methacrylate graft terpolymer EP rubber, maleic anhydride graft terpolymer EP rubber or n-butyl acrylate grafting ethylene-propylene-diene monomer;
Described mineral filler is white carbon black, potter's clay, talcum powder, calcium carbonate, magnesiumcarbonate, aluminum oxide or its mixture;
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt;
Described free radical photo-initiation is that the interior cracking type of molecule is or/and intermolecular hydrogen-capture-type light initiator;
Described multi-group crosslink agent is triallyl cyanurate, cyamelide triallyl, hydroxymethyl-propane three (methyl) acrylate, trimethylolpropane tris allyl ether, tetramethylolmethane three allyl ethers, tetramethylolmethane tetraene propyl ether or its mixture;
Described composite antioxidant is phenols, phosphorous acid esters, phosphoric acid ester or the composite antioxidant that contains the thioesters kind antioxidant; Wherein phenolic antioxidant is 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) or four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphorous acid esters or phosphoric acid ester oxidation inhibitor are triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, the different monooctyl ester of tricresyl phosphite or tricresyl phosphate benzene methyl; The described thioesters kind antioxidant that contains is Tyox B, thio-2 acid bay octadecyl ester or thio-2 acid two (13) ester;
Described tenderizer is low molecular weight polyethylene, aromatic hydrocarbon oil, naphthenic oil, paraffin oil or microcrystalline wax;
Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane and/or two-(the silica-based propyl group of γ-triethoxy) tetrasulfide.
2. ultraviolet deep-crosslinked EPT rubber cable insulation or the sheath material of root a tree name claim 1 is characterized in that described cation light initiator is cationic photoinitiator, triphenyl hexafluoro-antimonic acid sulfosalt or two dodecylbenzene hexafluoroarsenate salt compounded of iodine;
Described free radical photo-initiation is benzoin dimethylether, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, Alpha-hydroxy phenyl isopropyl ketone, dialkoxy methyl phenyl ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone, benzophenone, 2-chlorobenzophenone, 4-chlorobenzene ketone, 4,4-dichloro benzophenone, dodecyl benzophenone, Oxoxanthone or anthraquinone Fluorenone;
Described composite antioxidant is phenolic antioxidant and phosphorous acid esters or contains the composite composite antioxidant of thioesters class.
3. ultraviolet deep-crosslinked EPT rubber cable insulation or the sheath material of root a tree name claim 2, it is characterized in that described composite antioxidant is that four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and triphenyl phosphite or tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or the composite composite antioxidant of Tyox B.
4. a claim 1 or 2 or 3 ultraviolet deep-crosslinked EPT rubber cable insulation or the sheath material method for preparing cable insulation or restrictive coating, it is characterized in that with terpolymer EP rubber and graft modification terpolymer EP rubber as base-material, by 100 parts of base-material gross weights, add mineral filler 100-180 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.5-5.0 weight part, multi-group crosslink agent 0.5-5.0 weight part, composite antioxidant 0.01-1.0 weight part, tenderizer 5.0-10.0 weight part, after silane coupling agent 0.5-5.0 weight part mixes, at 100-150 ℃ of mixing 8-10 minute, extrude through twin screw extruder again and make photo-crosslinking EPT rubber cable material; Then melt extrude this EPT rubber cable material of coating at conductive cable cores and become insulation layer or restrictive coating, immediately at light intensity 400-4000mW/cm
2, wavelength 200-500nm and light distribution thereof and above-mentioned cationic photopolymerization initiator system be complementary, can adopt respectively and be equipped with that thermoelectron excites middle pressure mercuryarc lamp or the microwave-excitation Non-polarized lamp that is equipped with the H type, is added with the D type of ferro element or is added with the V-type of gallium element is in the ultraviolet light irradiation cross-linking apparatus of specific light source insulation layer or restrictive coating to be carried out melting attitude on-line continuous ultraviolet light irradiation 0.5-20 second, evenly be cross-linked into EPT rubber cable insulation layer or restrictive coating to reach the degree of depth.
5. the ultraviolet deep-crosslinked EPT rubber cable insulation of root a tree name claim 4 or sheath material prepare the method for cable insulation or restrictive coating, it is characterized in that described terpolymer EP rubber is that the 3rd monomer is the H type terpolymer EP rubber that the E type terpolymer EP rubber of vinylidene norbornylene, D type terpolymer EP rubber that the 3rd monomer is dicyclopentadiene or the 3rd monomer are Isosorbide-5-Nitrae-hexadiene;
Described graft modification terpolymer EP rubber is glycidyl methacrylate graft terpolymer EP rubber, maleic anhydride graft terpolymer EP rubber or n-butyl acrylate grafting ethylene-propylene-diene monomer;
Described mineral filler is white carbon black, potter's clay, talcum powder, calcium carbonate, magnesiumcarbonate, aluminum oxide or its mixture;
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt;
Described free radical photo-initiation is that the interior cracking type of molecule is or/and intermolecular hydrogen-capture-type light initiator;
Described multi-group crosslink agent's triallyl cyanurate, cyamelide triallyl, hydroxymethyl-propane three (methyl) acrylate, trimethylolpropane tris allyl ether, tetramethylolmethane three allyl ethers, tetramethylolmethane tetraene propyl ether or its mixture;
Described composite antioxidant is phenols, phosphorous acid esters, phosphoric acid ester or contains the thioesters kind antioxidant; Wherein phenolic antioxidant comprises 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) or four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester; Described phosphorous acid esters or phosphoric acid ester oxidation inhibitor comprise triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester, the different monooctyl ester of tricresyl phosphite or tricresyl phosphate benzene methyl; The described thioesters kind antioxidant that contains comprises Tyox B, thio-2 acid bay octadecyl ester or thio-2 acid two (13) ester;
Described tenderizer is low molecular weight polyethylene, aromatic hydrocarbon oil, naphthenic oil, paraffin oil or microcrystalline wax;
Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane and/or two-(the silica-based propyl group of γ-triethoxy) tetrasulfide.
6. the ultraviolet deep-crosslinked EPT rubber cable insulation of root a tree name claim 5 or sheath material prepare the method for cable insulation or restrictive coating, it is characterized in that described cation light initiator is phosphofluoric acid triaryl sulfonium salts, cationic photoinitiator, triphenyl hexafluoro-antimonic acid sulfosalt or two dodecylbenzene hexafluoroarsenate salt compounded of iodine;
Described free radical photo-initiation is benzoin dimethylether, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, Alpha-hydroxy phenyl isopropyl ketone, acyl group phosphorous oxides photoinitiator, dialkoxy methyl phenyl ketone, 1-hydroxyl-cyclohexyl-phenyl ketone or 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone, benzophenone, 2-chlorobenzophenone; Described composite antioxidant is phenolic antioxidant and phosphorous acid esters or contains the composite composite antioxidant of thioesters kind antioxidant.
7. the ultraviolet deep-crosslinked EPT rubber cable insulation of root a tree name claim 6 or sheath material prepare the method for cable insulation or restrictive coating, it is characterized in that described composite antioxidant is that four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and triphenyl phosphite or tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or the composite composite antioxidant of Tyox B.
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| CN105820438B (en) * | 2016-04-27 | 2018-08-07 | 安徽中鼎橡塑制品有限公司 | A kind of motor turning dust cover thermoplastic vulcanizate material and preparation method thereof |
| CN105860284B (en) * | 2016-04-27 | 2018-08-07 | 安徽中鼎橡塑制品有限公司 | A kind of motor turning dust cover thermoplastic vulcanizate material and preparation method thereof |
| CN108299742B (en) | 2017-01-13 | 2021-04-06 | 杭州星庐科技有限公司 | Photo-crosslinked rubber composition, use thereof, and method for producing the use |
| WO2019000592A1 (en) * | 2017-06-29 | 2019-01-03 | 虞春艳 | Cable insulating material |
| CN109265861A (en) * | 2018-08-31 | 2019-01-25 | 安庆市泽烨新材料技术推广服务有限公司 | Network system cable sheath material and preparation method thereof |
| CN109721861B (en) * | 2018-12-28 | 2021-09-07 | 四川省威盾匠心建设有限公司 | Photosensitive self-crosslinking ethylene propylene diene monomer waterproof roll and preparation method thereof |
| CN114566320A (en) * | 2019-06-20 | 2022-05-31 | 广西纵览线缆集团有限公司 | High-toughness optical fiber composite cable |
| CN114276609B (en) * | 2019-06-20 | 2023-02-28 | 广西纵览线缆集团有限公司 | Preparation process of fire-resistant safety cable |
| CN113980301A (en) * | 2021-11-12 | 2022-01-28 | 上海凯波电缆特材股份有限公司 | Ultraviolet irradiation crosslinking high-electrical-property charging pile insulated cable material for electric automobile and preparation method thereof |
| CN114085482B (en) * | 2021-12-13 | 2024-03-22 | 哈尔滨理工大学 | Ultraviolet light crosslinked low-voltage ethylene propylene rubber insulating material and preparation method thereof |
| CN115424784A (en) * | 2022-08-24 | 2022-12-02 | 东莞市民兴电缆有限公司 | Preparation process of irradiation type rubber sleeve cable |
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| US5476748A (en) * | 1992-12-21 | 1995-12-19 | Ciba-Geigy Corporation | Photosensitive compositions |
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Effective date of registration: 20181115 Address after: No. 7, Zhonghua Road, Dongfeng High-tech Industrial Development Zone, Jiamusi City, Heilongjiang Province, 154000 Patentee after: Honglongjiang Orient Science & Technology Co., Ltd. Address before: No. 34 Cixi Road, Shuyang County, Jiangsu Province Co-patentee before: Honglongjiang Orient Science & Technology Co., Ltd. Patentee before: Muyang Youwei New Material Co., Ltd. |