CN102153802A - Ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable material and method for preparing ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer from same - Google Patents
Ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable material and method for preparing ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer from same Download PDFInfo
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Abstract
The invention relates to ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable material and a method for preparing an ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer from the same. The method comprises the following steps: adding a metal hydroxide flame retardant, a cationic photoinitiator, a free radical photoinitiator, a multi-functional cross-linking agent, a compound antioxidant, a flame-retardant synergist, a synergistic smoke suppressant and a processing aid to polyethylene or grafted and modified polyethylene and/or ethylene vinyl acetate or grafted and modified copolymer thereof which are used as base materials, compounding, mixing the materials uniformly according to the proportion, granulating, extruding to prepare the ultraviolet-light cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer, and immediately irradiating with a specific ultraviolet-light source to obtain the deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer. The cross-linking equipment used for preparing the novel material by using a novel technology has low investment, and the process is simple and environmental friendly, saves energy, ensures high production efficiency and low cost and good quality of product and can be widely used for producing high-performance special wire and cable products and the like.
Description
Technical field
The invention belongs to cross-linking flame-retardant polyolefin electric wire and cable technical field, particularly relate to the preparation method of UV-light degree of depth crosslinked halogen-free flame-retardant cable material of polyolefin (referring to cable insulating material or sheath material) and insulation layer or restrictive coating.
Background technology
The cross-linked polyolefin material has characteristics such as electrical property excellence, life-time service temperature height, corrosion-resistant, withstand voltage resistance toheat are good, physical strength height, just more and more insulation and sheath materials that are applied to make cross-linked wire and cable.But the main drawback of cross-linked polyolefin material be easily fire burns cause fire.And the halogen-containing flame retardant polyolefine material of the most normal use at present can discharge poisonous, obnoxious flavoures such as a large amount of smog and corrosive hydrogen halides when burning, hinders people to withdraw from fire and fire-fighting work, has caused the heavy losses of life and property.On the other hand, phosphonium flame retardant also can pollute disaster to environment.Therefore, exploitation low-smoke halogen-free phosphor-free fire retardant material new technology and the application in cross-linked wire and cable thereof have become a kind of inexorable trend of development.
It is that the material system of composition is at preparation crosslinked halogen-free flame-retardant polyolefin cable under the crosslinked condition of high-energy electron beam irradiation or under the chemically crosslinked condition at the superoxide thermal initiation that Chinese patent application numbers 98126595.2 discloses with PE, EVA, metal hydroxides, red phosphorus, carbon black, linking agent, the limiting oxygen index(LOI) of goods is 41%, tensile strength is 11MPa, and elongation at break is 450%.Chinese patent application number 200510102257.9 blend systems that disclose based on EVA, ethylene-octene copolymer (POE), magnesium hydroxide, linking agent prepare the halogen-free anti-flaming polyolefin cable material with the high-energy electron beam irradiation crosslinking, the oxygen index of goods is greater than 32%, good mechanical performance.Chinese patent application number 00112600.8 discloses with silane cross-linking methods such as polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), magnesium hydroxide, vinylsiloxane, silane hydrolyzate crosslinking catalysts and has prepared the halogen-free phosphorus-free inflaming retarding polyolefine cable, the limiting oxygen index(LOI) of goods reaches 32.5%, and tensile strength and elongation at break reach 12.8MPa and 426% respectively.U.S. Pat 6227908B1 discloses the co-mixing system crosslinked halogen-free anti-flaming polyolefin cable material of peroxide crosslinking method based on EVA, magnesium hydroxide, polymer-compatible agent, silicone resin, carbon black, linking agent, can obtain higher oxygen index value under the addition of less relatively magnesium hydroxide, the mechanical property of system is improved simultaneously.Yet the facility investment of the high-energy radiation crosslinking in above-mentioned each method is higher, the comparatively complicated and protection condition harshness of Operation and Maintenance, and owing to its process characteristic only is fit to do the electric wire that less line electric wire directly is not suitable for doing big line footpath; Superoxide chemically crosslinked rule needs the longer curing tube of High Temperature High Pressure, and investment is big, and energy utilization rate is low, and technology is comparatively complicated, and is not suitable for the production of less line footpath electric wire; And silane cross-linking method relates to hydrolysis reaction, the poor stability of goods, and withstand voltage temperature resistant grade is also lower.
In recent years, the applicant has invented a kind of novel uv cross-linking method (Chinese invention patent publication number: CN 1218963 and CN 1919571), and the industrialization production that has dropped into cross-linked wire and cable.This new technology has special advantages: required cross-linking apparatus investment is low, technology simple, convenient operating maintenance, the cost of energy-conserving and environment-protective, production efficiency height, product is low, high-temperature stability and good mechanical performance, simultaneously owing to adopting UV-light, applicable to making the not photo-crosslinking electric wire product in collinear footpath as irradiation source.Recently, the applicant has described with PE, EVA, phosphorus-nitrogen expansion type fire retardant, free radical photo-initiation and linking agent etc. and has carried out insulation and the sheath material that uv cross-linking method prepares photo-crosslinking expansion type phosphor nitrogen class fire retardant polyolefin cable in Chinese patent application numbers 200810023192.2, its goods flame retardant properties and good mechanical performance, oxygen index is greater than 30%, the vertical combustion experiment is by UL-94 V-0 level, tensile strength is greater than 12MPa, elongation at break is greater than 350%, and volume specific resistance is greater than 2 * 10
13Ω .cm, heat aging performance is good, and melt viscosity is low, and processing characteristics is better.In Chinese patent application numbers 200910116279, it is that the EPDM rubber of main flame retardant carries out ultraviolet light cross-linking and prepares cross-linking flame-retardant EPDM cable insulation and sheath material with the metal hydroxides under the light initiation system of free radical photo-initiation and linking agent that the applicant discloses again, and its product properties is good.The expansion type phosphor nitrogen based flame retardant of comparing, advantages such as that metal hydroxides has is cheap, non-halogen non-phosphate smoke elimination environmental protection, but need the addition of 100-180% just can meet the requirements of flame retardant effect usually because its flame retarding efficiency is low, therefore the consistency that adds metal hydroxides and matrix resin is relatively poor, has also brought the serious deterioration of mechanical property and has extruded shortcoming such as processing difficulties.Yet, find in the actual use of above-mentioned two patent applications: what no matter add is the expansion type phosphor nitrogen based flame retardant, still metal hydroxides mineral filler, except serious deterioration the mechanical property and processing characteristics of polymeric matrix, what cause bigger 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 the use properties and the range of application of fire retardant material.Therefore, how to overcome and add the above-mentioned shortcoming that halogen-free flame retardants brings, improve the penetration depth and the photo-initiated crosslinking efficient of UV-light in big addition Halogenless fire retarded polymer matrix material and become the key technical problem that develops the crosslinking halogen-free flame-retardant material.
The polymkeric substance ultraviolet light cross-linking mainly adopts two photoinitiators: the most normally used at present class is a radical initiator, as hydrogen-capture-type light initiator benzophenone (BP) class and crack type photoinitiator benzoin dimethylether (BDK) etc., produce free radical after the absorption UV-light and cause crosslinking reaction, but since the penetration power of UV-light a little less than, the deep layer that especially is difficult to be penetrated into material in containing the thicker sample of mineral filler causes the radical crosslinking reaction.Yet another kind of very important light trigger is a cation light initiator, and a small amount of application is only arranged in the coating curing field at present.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the above-mentioned photo-crosslinking prior art, the contriver is surprised in secular electric wire development research and production practice to find that novel light initiation system that cation light initiator and free radical photo-initiation combine is at light intensity 400-4000mW/cm
2Carry out melting attitude on-line continuous ultraviolet light irradiation under the specific ultraviolet source condition that wavelength 200-500nm and intensity of emission spectra distribution thereof and cation light initiator absorption spectrum and intensity distribution are complementary and obtain the crosslinked unusual effect of the degree of depth, simultaneously in the bittern-free flame-proof material formula system, be used grafted polyolefinic resin, the Ya Nami of surface modification or nano level metal oxyhydroxide, various complex art means such as retardant synergist and smoke suppressor solve UV-light in big addition bittern-free flame-proof material deep layer penetrativity difference and cause the key technical problem of the serious deterioration etc. of the mechanics of materials and processing characteristics, exploitation provides a kind of cross-linking apparatus investment low, technology is simple, energy-conserving and environment-protective, the production efficiency height, the product cost inferior quality is good, can reach UV-light degree of depth crosslinked halogen-free flame-retardant (referring to that low-smoke halogen-free phosphor-free the is fire-retardant) cable material of polyolefin (referring to insulation or sheath material) of the even ultraviolet light cross-linking of the degree of depth and the preparation method of insulation layer or restrictive coating thereof.
UV-light degree of depth cross-linked low-smoke halogen-free phosphor-free flame-retardant polyolefin cable insulation provided by the invention or sheath material, it is characterized in that with polyethylene or graft modification polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by 100 parts of base-material gross weights, add metal hydroxide combustion inhibitor 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, be equipped with retardant synergist 0.5-5.0 weight part, synergistic smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 weight part combine.
UV-light degree of depth cross-linked low-smoke halogen-free phosphor-free flame-retardant polyolefin cable insulation provided by the invention or sheath material are prepared into the method for cable insulation or restrictive coating, it is characterized in that: with polyethylene or graft modification polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by 100 parts of base-material gross weights, add metal hydroxide combustion inhibitor 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, retardant synergist 0.5-5.0 weight part, after synergistic smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 weight part mix, become the photo-crosslinking fire-resistant cable material at 140-200 ℃ of extruding pelletization; On the cable conduction core, melt extrude this fire-resistant cable material of coating then 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 to be equipped with in the ultraviolet light irradiation cross-linking apparatus that V-type lamp that thermoelectron presses mercuryarc lamp or electrodeless lamp of middle pressure microwave-excitation such as H type lamp in exciting, is added with the D type lamp of ferro element and is added with gallium element is a specific light source insulation layer or restrictive coating are carried out melting attitude on-line continuous ultraviolet light irradiation 0.5-20 second, evenly be cross-linked into cable insulation or restrictive coating to reach the degree of depth.
UV-light degree of depth cross-linked low-smoke halogen-free phosphor-free flame-retardant polyolefin cable insulation provided by the invention or sheath material and be prepared into cable insulation or the method for restrictive coating in, described polyethylene is new LDPE (film grade) (LDPE), LLDPE (LLDPE), high density polyethylene(HDPE) (HDPE); Described graft modification polyethylene is glycidyl methacrylate graft polyethylene or maleic anhydride grafted polyethylene; Described ethylene vinyl acetate (EVA) is the EVA of 14-80%VA content; The graft modification multipolymer of described ethylene vinyl acetate is glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride grafted ethene vinyl acetate copolymer or acid amide-grafted ethylene vinyl acetate copolymer.
Described metal hydroxide combustion inhibitor is surfactant-modified or unmodified micron order, Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide, magnesiumcarbonate, calcium hydroxide or layered double-hydroxide (claiming hydrotalcite again), is preferably surfactant-modified Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide or layered double-hydroxide.
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt (or claiming an iron arene salt) class etc., for example 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, two dodecylbenzene hexafluoroarsenate salt compounded of iodine, phosphofluoric acid triaryl sulfonium salts, triphenyl hexafluoro-antimonic acid sulfosalt, ferrocene-4-fluoroborate or fragrant luxuriant iron hexafluorophosphate etc.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 cationic photo-initiated crosslinking generally is not subjected to sample to stop the influence of illumination or thickness of sample, because cationoid reaction has produced new cation activity center again on polymer chain in the chain transfer termination reaction, can in stopping the polymeric matrix deep layer position that ultraviolet lighting or UV-light can't arrive, continue to cause the enhanced crosslinking reaction, that is to say, cationic photopolymerization is crosslinked to be 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.The main absorption spectrum of salt cation light initiator concentrates on usually less than 300nm wave band district, and the main absorption spectrum of ferrocene salt cationoid light trigger is then usually greater than 360nm wave band district.But press the mercuryarc lamp or the emmission spectrum scope of the electrodeless lamp of microwave-excitation and the main absorption spectrum and the intensity distribution scope of intensity distribution and these cation light initiators thereof not exclusively to mate at present normally used, 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 " not exclusively coupling " problem: the light initiation system that one adopts cation light initiator to match with free radical photo-initiation, 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 the absorbing wavelength and the intensity distribution thereof of corresponding cation light initiator.For example, the cation light initiator that absorbing wavelength is concentrated on less than 300nm just can adopt the electrodeless lamp of H type microwave-excitation, 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 microwave-excitation D type or the V-type lamp that has added metallic elements of ferrum or gallium respectively.The D type lamp that adds ferro element in the mercury lamp can make the ultraviolet ray intensity of 320-400nm place output obviously increase, when the V-type lamp that adds gallium element then can make the very high ultraviolet light intensity of 405-440nm place output.Can change the emmission spectrum and the intensity distribution scope thereof of ultraviolet lamp by interpolation metallic elements of ferrum or gallium, so that cooperate the 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-crosslinking efficient.
Described free radical photo-initiation is one or more combinations in benzoin dimethylether (BDK), dialkoxy methyl phenyl ketone, Oxoxanthone, anthraquinone, Fluorenone or benzophenone (BP) and the derivative thereof.
Described multi-group crosslink agent is triallyl cyanurate (TAC), cyamelide triallyl (TAIC), trimethylolpropane tris (methyl) acrylate (TMPTA), trimethylolpropane tris allyl ether (TMPAE), tetramethylolmethane three allyl ethers (PETAE), tetramethylolmethane tetraene propyl ether or triglycol methacrylic ester (TEGMA), or its mixture.
Described composite antioxidant is by two or more phenols, phosphorous acid esters, phosphoric acid ester or contain the thioesters kind antioxidant and form composite antioxidant, is preferably phenolic antioxidant and phosphorous acid esters or contains the combination of thioesters class; Described phenolic antioxidant is 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol (oxidation inhibitor 246), 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) (antioxidant 300) or four [methylene radical-3-(3 ', 5 '-di-tert-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010); Described phosphorous acid esters or phosphoric acid ester oxidation inhibitor are triphenyl phosphite (TPP), tricresyl phosphite (2,4-di-tert-butyl phenyl) ester (oxidation inhibitor 168), the different monooctyl ester of tricresyl phosphite (TIOP) or tricresyl phosphate benzene methyl; The described thioesters kind antioxidant that contains is Tyox B (DLTP), thio-2 acid bay octadecyl ester (LSTP) or thio-2 acid two (13) ester (DTDTP); [methylene radical-3-(3 ' for You Yisi, 5 '-di-tert-butyl-4 '-hydroxy phenyl) propionic acid] cooperation of pentaerythritol ester (antioxidant 1010) and triphenyl phosphite (TPP), tricresyl phosphite (2,4-di-tert-butyl phenyl) ester (oxidation inhibitor 168) or Tyox B (DLTP) is good.
Described retardant synergist is zinc borate, superfine zinc borate, ferrocene, polynite, silicon-dioxide, aerosil, silica gel, zinc silicate, organosilicon compound, transition metal oxide or trimeric cyanamide and derivative thereof.
Described synergistic smoke suppressor is molybdenum sesquioxide, Ammonium Heptamolybdate or ammonium octamolybdate.
Described processing aid is lipid acid and metal-salt and/or silicoorganic compound, as sodium stearate, Magnesium Stearate, Zinic stearas or calcium stearate and polydimethylsiloxane, silicone resin or hydroxy silicon oil.
Described specific ultraviolet source is that thermoelectron excites mercuryarc lamp and the electrodeless lamp two big class medium pressure mercury lamps of microwave-excitation, and wherein the electrodeless lamp of microwave-excitation 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.Can change the emmission spectrum and the intensity distribution scope thereof of ultraviolet lamp by interpolation metallic elements of ferrum or gallium, so that cooperate the 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-crosslinking efficient.
The UV-light degree of depth provided by the invention { layer } insulation of cross-linked low-smoke halogen-free phosphor-free fire retardant polyolefin cable and sheath material and insulation layer or restrictive coating preparation method's characteristics are to adopt the novel light initiation system that cation light initiator combines with free radical photo-initiation and cooperate the selected specific ultraviolet source of cation light initiator to carry out ultraviolet light irradiation cross-linking and be used various complex art means such as grafted polyolefinic resin in the bittern-free flame-proof material formula system to solve the deep layer penetrativity difference of UV-light in big addition bittern-free flame-proof material and cause key technical problems such as the mechanics of materials and the serious deterioration of processing characteristics, and it is low to provide a kind of cross-linking apparatus to invest, technology is simple, energy-conserving and environment-protective, the production efficiency height, the measured production technology of new generation of product cost low-quality is made evenly crosslinked low-smoke halogen-free phosphor-free fire retardant polyolefin insulated wire cable of the UV-light degree of depth.
Compare with original crosslinking halogen-free flame-retardant cable technology, because 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 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 influence of thickness of sample, because cationoid reaction has produced new cation activity center again on polymer chain in the chain transfer termination reaction, can in stopping the polymeric matrix deep layer position that ultraviolet lighting or UV-light can't arrive, continue to cause enhanced crosslinking reaction (also claiming dark reaction).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 and could produce the shortcoming of crosslinking reaction after using free radical photo-initiation must absorb UV-light merely in the former Chinese patent application numbers 200810023192.2 and 200910116279, be difficult to be penetrated into a difficult problem that contains a large amount of bittern-free flame-proof materials initiation deep layer crosslinking reactions a little less than thereby efficiently solve the UV-light penetration power.
Compare with the ultraviolet source that uses in original crosslinking halogen-free flame-retardant cable technology, ultraviolet light irradiation cross-linking apparatus of the present invention has been selected light intensity 400-4000mW/cm for use
2, the specific ultraviolet source that is complementary of wavelength 200-500nm and intensity distribution thereof and cationic photopolymerization initiator system absorption spectrum and intensity distribution thereof, so that the cationic photopolymerization initiator system absorbs more UV-light energy, at utmost improve its light-initiated efficient and crosslinked ability of deep layer in the halogen-free anti-flaming polyolefin material, thereby the even photo-crosslinking degree of depth of halogen-free anti-flaming polyolefin material is brought up to more than the 3.0mm from original not enough 1.5mm, and obviously improved mechanical property, flame retardant properties and the heat aging performance of material.
, chemically crosslinked crosslinked with existing traditional high-energy radiation prepares the halogen-free anti-flaming polyolefin cable material with the crosslinked with silicane technology and compares, UV-light degree of depth cross-linked low-smoke halogen-free phosphor-free flame-retardant polyolefin cable insulation of the present invention and sheath material and preparation method thereof have the unique technique advantage: the investment of required cross-linking apparatus is low, technology simple, convenient operating maintenance, and the cost inferior quality of energy-conserving and environment-protective, production efficiency height, product is good; Owing to adopted the ultra-fine or nano level flame retardant and other auxiliary agent that add polyolefin graft polymers and surface modification, improved greatly fire retardant dispersed in matrix resin and with the consistency of matrix resin, greatly promoted flame retardant properties, mechanics electric property, processing characteristics and the heat aging property of material product.
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
Take by weighing 80 parts of EVA (VA content 18wt%) by weight, 10 parts of glycidyl methacrylate graft polyethylene, 10 parts of maleic anhydride grafted polyethylenes, 150 parts of magnesium hydroxides, 4,2.5 parts of 4 '-dimethyl diphenyl iodine phosphoric acid salt, 0.5 part of 4-chlorobenzophenone, 1.5 parts of TMPTA, 0.3 part of antioxidant 300,0.15 part of TPP, 2 parts of zinc borates, 10 parts of molybdenum sesquioxides, 3 parts of hydroxy silicon oils; Each material component is after mixing, at 160 ℃ of extruding pelletizations; On the cable conduction core, melt extrude this flame-proof material of coating then and become 3.0mm 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 immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of H type microwave-excitation is light source, crosslinking time is 5 seconds.Experimental result shows: the tensile strength of UV-light degree of depth cross-linking flame-retardant polyolefin cable material is 15.6MPa, elongation at break 220%, and hot unit elongation 50%, oxygen index 43%, volume specific resistance are 3.2 * 10
13Ω .m can be by the thermal ageing test of 145 ℃ * 168h.
Comparative example 1
Do not adopt cation light initiator 4,4 '-dimethyl diphenyl iodine phosphoric acid salt but keep simultaneous test under light trigger parts by weight and the constant situation of other condition: take by weighing 80 parts of EVA (VA content 18wt%) by weight, 10 parts of glycidyl methacrylate graft polyethylene, 10 parts of maleic anhydride grafted polyethylenes, 150 parts of magnesium hydroxides, 3.0 parts of 4-chlorobenzophenones, 1.5 parts of TMPTA, 0.3 part of antioxidant 300,0.15 part of TPP, 2 parts of zinc borates, 10 parts of molybdenum sesquioxides, 3 parts of hydroxy silicon oils; Each material component is after mixing, at 160 ℃ of extruding pelletizations; On the cable conduction core, melt extrude this flame-proof material of coating then and become 3.0mm 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 immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of H type microwave-excitation is light source, crosslinking time is 5 seconds.Experimental result shows: the tensile strength of the ultraviolet light cross-linking fire retardant polyolefin cable material of preparation is 11.2MPa, elongation at break 280%, and hot elongation test can't be passed through, and oxygen index 41%, volume specific resistance are 2.1 * 10
13Ω .m can't be by the thermal ageing test of 145 ℃ * 168h.
Embodiment 2
Take by weighing 60 parts of EVA (VA content 28wt%) by weight, 20 parts of new LDPE (film grade)s, 10 parts of glycidyl methacrylate graft EVA, 10 parts of maleic anhydride graft EVA, 130 parts of ultra-fine level magnesium hydroxides, 3.5 parts of phosphofluoric acid triaryl sulfonium salts, 4 ', 1.2 parts of 4 '-dichloro benzophenones, 3 parts of TAIC, 0.2 part of antioxidant 1010,0.1 part of DLTP, 0 part of silica 1,8 parts of Ammonium Heptamolybdates, 2 parts of sodium stearate; Each material component mixes the back at 170 ℃ of extruding pelletizations, on the cable conduction core, melt extrude then and coat insulation layer or the restrictive coating that this flame-proof material becomes 2.4mm, insulation layer or restrictive coating are carried out the ultraviolet light irradiation cross-linking of melting attitude on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of H type microwave-excitation is light source, crosslinking time is 8 seconds.Experimental result shows: the tensile strength of the UV-light degree of depth cross-linking flame-retardant polyolefin cable material of present embodiment preparation is 16.3MPa, elongation at break 230%, and hot unit elongation 45%, oxygen index 42%, volume specific resistance are 2.8 * 10
13Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Embodiment 3
Take by weighing 80 parts of LLDPE by weight, 15 parts of maleic anhydride grafted polyethylenes, 5 parts of glycidyl methacrylate graft polyethylene, 125 parts of nano layered double hydroxides, 2.0 parts of ferrocene-4-fluoroborate, 1.5 parts of 4-chlorobenzophenones, 5 parts of TAIC, 0.3 part of antioxidant 1010,0.7 part of DTDTP, 5 parts of aerosils, 5 parts of ammonium octamolybdates, 1.5 parts of Zinic stearass; Each material component mixes the back at 158 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 1.5mm 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 immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of V-type microwave-excitation is light source, crosslinking time is 0.5 second.Experimental result shows: the tensile strength of the UV-light degree of depth cross-linking flame-retardant polyolefin cable material of present embodiment preparation is 15.8MPa, elongation at break 225%, and hot unit elongation 65%, oxygen index 41%, volume specific resistance are 2.5 * 10
13Ω .m is by the thermal ageing test of 145 ℃ * 168h.
Comparative example 2
Adopt the electrodeless lamp of V-type microwave-excitation of pressing in common in the mercuryarc lamp alternate embodiment 3 and crosslinking time to be increased to 15 seconds and contrast experiment under the constant situation of other condition: to take by weighing 80 parts of LLDPE by weight, 15 parts of maleic anhydride grafted polyethylenes, 5 parts of glycidyl methacrylate graft polyethylene, 125 parts of nano layered double hydroxides, 2.0 parts of ferrocene-4-fluoroborate, 1.5 parts of 4-chlorobenzophenones, 5 parts of TAIC, 0.3 part of antioxidant 1010,0.7 part of DTDTP, 5 parts of aerosils, 5 parts of ammonium octamolybdates, 1.5 parts of Zinic stearass; Each material component mixes the back at 158 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 1.5mm insulation layer or restrictive coating, be the ultraviolet light irradiation cross-linking that in the ultraviolet light irradiation cross-linking apparatus of light source insulation layer or restrictive coating is carried out melting attitude on-line continuous to press mercuryarc lamp in common immediately, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the ultraviolet light cross-linking fire retardant polyolefin cable material of this comparative example preparation is 11.8MPa, elongation at break 275%, and heat is extended experiment and can't be passed through, and oxygen index 36%, volume specific resistance are 1.2 * 10
13Ω .m can't be by the thermal ageing test of 145 ℃ * 168h.
Embodiment 4
Take by weighing 80 parts of EVA (VA content 28wt%) by weight, glycidyl methacrylate graft EVA10 part, 10 parts of maleic anhydride graft new LDPE (film grade)s, 155 parts in aluminium hydroxide, 5 parts of two dodecylbenzene hexafluoroarsenate salt compounded of iodine, 4 parts of dodecyl benzophenone, 2.5 parts of TAC, 0.15 part of antioxidant 1010, DTDTP0.15 part, 1.5 parts of zinc silicates, 7 parts of ammonium octamolybdates, 1.5 parts of dimethyl silicone oils; Each material component mixes the back at 160 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 2.6mm 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 immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of H type microwave-excitation is light source, crosslinking time is 3.5 seconds.Experimental result shows: the tensile strength of the UV-light degree of depth cross-linking flame-retardant polyolefin cable material of present embodiment preparation is 16.6MPa, elongation at break 190%, and hot unit elongation 55%, oxygen index 41%, volume specific resistance are 4.2 * 10
13Ω .m is by the thermal ageing test of 145 ℃ * 168h.
Embodiment 5
Take by weighing 50 parts of LLDPE by weight, 20 parts of EVA (VA content 40wt%), 20 parts of acid amide-grafted ethylene vinyl acetate copolymers, 10 parts of glycidyl methacrylate graft EVA, 100 parts of nanometric magnesium hydroxides, 2.0 parts of fragrant luxuriant iron hexafluorophosphates, 1.0 parts of BP, 3.0 parts of TAIC, 0.2 part of antioxidant 1010, DLTP0.1 part, 4 parts of superfine zinc borates, 3 parts of polymethyl siloxanes, 8 parts of Ammonium Heptamolybdates, 4.0 parts of calcium stearates; Each material component mixes the back at 160 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 3.2mm 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 immediately in the ultraviolet light irradiation cross-linking apparatus that with the electrodeless lamp of D type microwave-excitation is light source, crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of the UV-light degree of depth cross-linking flame-retardant polyolefin cable material of present embodiment preparation is 17.6MPa, elongation at break 210%, and hot unit elongation 50%, oxygen index 42%, volume specific resistance are 4.4 * 10
13Ω .m is by the thermal ageing test of 135 ℃ * 168h.
Comparative example 3
Adopt the electrodeless lamp of D type microwave-excitation of pressing in common in the mercuryarc lamp alternate embodiment 5 and remain unchanged simultaneous test under the situation of crosslinking time and other condition: take by weighing 50 parts of LLDPE by weight, 20 parts of EVA (VA content 40wt%), 20 parts of acid amide-grafted ethylene vinyl acetate copolymers, 10 parts of glycidyl methacrylate graft EVA, 100 parts of nanometric magnesium hydroxides, 2.0 parts of the luxuriant iron hexafluorophosphates of virtue, 1.0 parts of BP, 3.0 parts of TAIC, 0.2 part of antioxidant 1010,0.1 part of DLTP, 4 parts of superfine zinc borates, 3 parts of polymethyl siloxanes, 8 parts of Ammonium Heptamolybdates, 4.0 parts of calcium stearates; Each material component mixes the back at 160 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 3.2mm insulation layer or restrictive coating, pressing mercuryarc lamp immediately in common is the ultraviolet light irradiation cross-linking that in the ultraviolet light irradiation cross-linking apparatus of light source insulation layer or restrictive coating is carried out melting attitude on-line continuous, and crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of the ultraviolet light cross-linking fire retardant polyolefin cable material of this comparative example preparation is 12.6MPa, elongation at break 270%, and hot elongation test can't be passed through, and oxygen index 39%, volume specific resistance are 2.4 * 10
13Ω .m can't be by the thermal ageing test of 135 ℃ * 168h.
Embodiment 6
Take by weighing 70 parts of EVA (VA content 18%) by weight, 15 parts of glycidyl methacrylate graft EVA, 15 parts of maleic anhydride grafted ethene vinyl acetate copolymers, 180 parts of magnesium hydroxides, 2.5 parts of triphenyl hexafluoro-antimonic acid sulfosalts, 1.5 parts of BP, 3.0 parts of TMPAE, 0.05 part of antioxidant 300,0.1 part of DLTP, 2 parts of polynites, 6 parts of molybdenum sesquioxides, 3 parts of hydroxy silicon oils; Each material component mixes the back at 165 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 1.6mm insulation layer or restrictive coating, be the ultraviolet light irradiation cross-linking that in the ultraviolet light irradiation cross-linking apparatus of light source insulation layer or restrictive coating is carried out melting attitude on-line continuous to press mercuryarc lamp in common immediately, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the UV-light degree of depth crosslinked halogen-free flame-retardant polyolefin cable material of present embodiment preparation is 13.4MPa, elongation at break 190%, and hot unit elongation 55%, oxygen index 47%, volume specific resistance are 3.3 * 10
13Ω .m is by the thermal ageing test of 145 ℃ * 168h.
Comparative example 4
Do not adopt cation light initiator triphenyl hexafluoro-antimonic acid sulfosalt but keep simultaneous test under light trigger parts by weight and the constant situation of other condition: take by weighing 70 parts of EVA (VA content 18%) by weight, 15 parts of glycidyl methacrylate graft EVA, 15 parts of maleic anhydride grafted ethene vinyl acetate copolymers, 180 parts of magnesium hydroxides, 4 parts of BP, 3.0 parts of TMPAE, 0.05 part of antioxidant 300,0.1 part of DLTP, 2 parts of polynites, 6 parts of molybdenum sesquioxides, 3 parts of hydroxy silicon oils; Each material component mixes the back at 165 ℃ of extruding pelletizations, on the cable conduction core, melt extrude this flame-proof material of coating then and become 1.6mm insulation layer or restrictive coating, be the ultraviolet light irradiation cross-linking that in the ultraviolet light irradiation cross-linking apparatus of light source insulation layer or restrictive coating is carried out melting attitude on-line continuous to press mercuryarc lamp in common immediately, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of the ultraviolet light cross-linking halogen-free anti-flaming polyolefin cable material of this comparative example preparation is 10.8MPa, elongation at break 240%, and hot elongation test can't be passed through, and oxygen index 41%, volume specific resistance are 1.3 * 10
13Ω .m can't be by the thermal ageing test of 145 ℃ * 168h.
Claims (4)
1. UV-light degree of depth crosslinked halogen-free flame-retardant polyolefin cable insulation or sheath material, it is characterized in that with polyethylene or graft modification polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by 100 parts of base-material gross weights, add metal hydroxide combustion inhibitor 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, be equipped with retardant synergist 0.5-5.0 weight part, synergistic smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 weight part are combined into;
Described polyethylene is new LDPE (film grade), LLDPE or high density polyethylene(HDPE); Described graft modification polyethylene is glycidyl methacrylate graft polyethylene or maleic anhydride grafted polyethylene; Described ethylene vinyl acetate copolymer is the ethylene vinyl acetate of 14-80%VA content; Described graft modification multipolymer is glycidyl methacrylate graft ethylene vinyl acetate copolymer, maleic anhydride grafted ethene vinyl acetate copolymer or acid amide-grafted ethylene vinyl acetate copolymer;
Described metal hydroxide combustion inhibitor is surfactant-modified or unmodified micron order, Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide, magnesiumcarbonate, calcium hydroxide or layered double-hydroxide;
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt;
Described free radical photo-initiation is one or more combinations in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, anthraquinone, Fluorenone or benzophenone and the derivative thereof;
Described multi-group crosslink agent is triallyl cyanurate, cyamelide triallyl, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, tetramethylolmethane three allyl ethers, tetramethylolmethane tetraene propyl ether or triglycol methacrylic ester, or its mixture;
Described composite antioxidant serve as reasons two or more phenols, phosphorous acid esters, phosphoric acid ester or contain the composite antioxidant that the thioesters kind antioxidant is formed, wherein said phenolic antioxidant is 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) or four [methylene radical-3-(3 ', 5 '-di-tert-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 retardant synergist is zinc borate, superfine zinc borate, ferrocene, polynite, silicon-dioxide, aerosil, silica gel, zinc silicate, organosilicon compound, transition metal oxide or trimeric cyanamide and derivative thereof;
Described synergistic smoke suppressor is molybdenum sesquioxide, Ammonium Heptamolybdate or ammonium octamolybdate;
Described processing aid is lipid acid and metal-salt and/or silicoorganic compound.
2. according to the UV-light degree of depth crosslinked halogen-free flame-retardant polyolefin cable insulation or the sheath material of claim 1, it is characterized in that described cation light initiator is 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, two dodecylbenzene hexafluoroarsenate salt compounded of iodine, phosphofluoric acid triaryl sulfonium salts, triphenyl hexafluoro-antimonic acid sulfosalt, ferrocene-4-fluoroborate or fragrant luxuriant iron hexafluorophosphate;
Described metal hydroxide combustion inhibitor is surfactant-modified Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide or layered double-hydroxide; Described processing aid is sodium stearate, Magnesium Stearate, Zinic stearas, calcium stearate, polydimethylsiloxane, silicone resin or hydroxy silicon oil; Described composite antioxidant is the composite antioxidant that four [methylene radical-3-(3 ', 5 '-di-tert-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol esters and triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or Tyox B cooperate.
3. the method that is prepared into cable insulation or restrictive coating according to the UV-light degree of depth crosslinked halogen-free flame-retardant polyolefin cable insulation or the sheath material of claim 1 or 2, it is characterized in that: with polyethylene or graft modification polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by 100 parts of base-material gross weights, add metal hydroxide combustion inhibitor 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, retardant synergist 0.5-5.0 weight part, after synergistic smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 weight part mix, become the photo-crosslinking fire-resistant cable material at 140-200 ℃ of extruding pelletization; On the cable conduction core, melt extrude this fire-resistant cable material of coating then and become insulation layer or restrictive coating, immediately at light intensity 400-4000mW/cm
2, wavelength 200-500nm and light distribution thereof and described cation light initiator system be complementary, adopt and be equipped with that thermoelectron is pressed mercuryarc lamp in exciting or the electrodeless lamp of microwave-excitation that H type lamp is housed, is added with the D type lamp of ferro element or is added with the V-type lamp 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 respectively, evenly be cross-linked into cable insulation or restrictive coating to reach the degree of depth;
Described polyethylene is new LDPE (film grade), LLDPE, high density polyethylene(HDPE); Described graft modification polyethylene is glycidyl methacrylate graft polyethylene or maleic anhydride grafted polyethylene;
Described ethylene vinyl acetate is the ethylene vinyl acetate of 14-80%VA content; The graft modification multipolymer of described ethylene vinyl acetate is glycidyl methacrylate graft ethylene vinyl acetate copolymer or maleic anhydride grafted ethene vinyl acetate copolymer or acid amide-grafted ethylene vinyl acetate copolymer;
Described metal hydroxide combustion inhibitor is surfactant-modified or unmodified micron order, Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide, magnesiumcarbonate, calcium hydroxide or layered double-hydroxide;
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt;
Described free radical photo-initiation is one or more combinations in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, anthraquinone, Fluorenone or benzophenone and the derivative thereof;
Described multi-group crosslink agent is triallyl cyanurate, cyamelide triallyl, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, tetramethylolmethane three allyl ethers, tetramethylolmethane tetraene propyl ether or triglycol methacrylic ester, or its mixture;
Described composite antioxidant two or more phenols of serving as reasons, phosphorous acid esters, phosphoric acid ester or contain the thioesters kind antioxidant and form composite antioxidant, wherein said phenolic antioxidant is 2, the 6-di-tert-butylphenol, 2,4, the 6-tri-tert-butylphenol, 4,4 '-thiobis (6-tertiary butyl-3-methylphenol) or four [methylene radical-3-(3 ', 5 '-di-tert-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, different monooctyl ester of tricresyl phosphite or tricresyl phosphate benzene methyl, the described thioesters kind antioxidant that contains is a Tyox B, thio-2 acid bay octadecyl ester or thio-2 acid two (13) ester;
Described retardant synergist is zinc borate, superfine zinc borate, ferrocene, polynite, silicon-dioxide, aerosil, silica gel, zinc silicate, organosilicon compound, transition metal oxide or trimeric cyanamide and derivative thereof;
Described synergistic smoke suppressor is molybdenum sesquioxide, Ammonium Heptamolybdate or ammonium octamolybdate;
Described processing aid is lipid acid and metal-salt and/or silicoorganic compound.
4. the method that is prepared into cable insulation or restrictive coating according to the UV-light degree of depth crosslinked halogen-free flame-retardant polyolefin cable insulation or the sheath material of claim 3 is characterized in that described metal hydroxide combustion inhibitor is surfactant-modified Subnano-class or nanometric magnesium hydroxide, aluminium hydroxide or layered double-hydroxide;
Described cation light initiator is 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, two dodecylbenzene hexafluoroarsenate salt compounded of iodine, phosphofluoric acid triaryl sulfonium salts, triphenyl hexafluoro-antimonic acid sulfosalt, ferrocene-4-fluoroborate or fragrant luxuriant iron hexafluorophosphate;
Described composite antioxidant is the cooperation of four [methylene radical-3-(3 ', 5 '-di-tert-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol esters and triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or Tyox B;
Described processing aid is sodium stearate, Magnesium Stearate, Zinic stearas or calcium stearate and polydimethylsiloxane, silicone resin or hydroxy silicon oil.
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