CN102161793B - Ultraviolet deep-crosslinked expansion flame-retardant polyolefine cable material, and preparation method of insulating or jacket layer thereof - Google Patents
Ultraviolet deep-crosslinked expansion flame-retardant polyolefine cable material, and preparation method of insulating or jacket layer thereof Download PDFInfo
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Abstract
The invention relates to an ultraviolet deep-crosslinked expansion phosphorus-nitrogen flame-retardant polyolefine cable material, and a preparation method of an insulating or jacket layer thereof. Polyethylene or graft-modified polyethylene and/or ethylene-vinyl acetate or graft-modified copolymer thereof are used as base materials, surface-modified expansion phosphorus-nitrogen halogen-free flame retardant, cation photoinitiator, free-radical photoinitiator, polyfunctional group crosslinking agent and composite antioxidant are added, and flame-retardant synergist, synergistic smoke suppressor and processing assistant are matched to obtain the ultraviolet deep-crosslinked expansion phosphorus-nitrogen flame-retardant polyolefine cable material. The preparation method comprises the following steps: proportionally and evenly mixing the materials to obtain granules, extruding to obtain an optical crosslinked expansion flame-retardant wire cable insulating layer or jacket layer, and radiating by a specific ultraviolet source for several seconds to obtain the deep-crosslinked insulating layer or jacket layer. The new material and new technology have the advantages of low investment required for crosslinking equipment, simple technique, energy saving, environmental protection, high production efficiency, low cost and good product quality, and can be widely used for manufacturing rail transportation cables, various mechanical wires, indoor assembly wires and the like.
Description
Technical field
The invention belongs to cross-linking flame-retardant polyolefin electric wire and cable preparing technical field, particularly relate to the preparation method of ultraviolet deep-crosslinked expansion (type P-N type) flame-proof polyolefine cable material and insulation layer or restrictive coating.
Background technology
Crosslinked polyolefin materials has excellent electrical property, life-time service temperature is high, corrosion-resistant, pressure-and heat-resistance performance is good, physical strength high, just more and more insulation or restrictive coating being applied to manufacture cross-linked wire and cable.But the main drawback of crosslinked polyolefin materials is easy ignition causes fire.And the halogen-containing flame retardant polyolefine material the most often used at present can discharge poisonous, the obnoxious flavoures such as a large amount of smog and corrosive hydrogen halides when burning, people are hindered to withdraw from fire and fire-fighting work.Therefore, exploitation bittern-free flame-proof material new technology and the application in cross-linked wire and cable thereof have become a kind of inexorable trend of development.
Chinese Patent Application No. 98126595.2 disclose with PE, EVA, metal hydroxides, red phosphorus, carbon black, linking agent for composition material system under high-energy electron beam irradiation cross linking conditions or under the chemically crosslinked condition of superoxide thermal initiation, prepare crosslinked halogen-free flame-retardant polyolefin cable, the limiting oxygen index(LOI) of goods is 41%, tensile strength is 11MPa, and elongation at break is 450%.Chinese Patent Application No. 200510102257.9 discloses prepares halogen-free anti-flaming polyolefin cable material based on the blend system high-energy electron beam irradiation crosslinking of EVA, ethylene-octene copolymer (POE), magnesium hydroxide, linking agent, the oxygen index of goods is greater than 32%, good mechanical performance.Chinese Patent Application No. 00112600.8 discloses prepares halogen-free phosphorus-free inflaming retarding polyolefine cable with silane cross-linking methods such as polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), magnesium hydroxide, vinylsiloxane, silane hydrolyzate crosslinking catalysts, the limiting oxygen index(LOI) of goods reaches 32.5%, and tensile strength and elongation at break reach 12.8MPa and 426% respectively.US Patent No. 6227908B1 discloses based on the crosslinked halogen-free anti-flaming polyolefin cable material of the co-mixing system peroxide crosslinking method of EVA, magnesium hydroxide, Its Compatibilizing Technology, silicone resin, carbon black, linking agent, can obtain higher oxygen index value under the addition of relatively less magnesium hydroxide, the mechanical property of system is improved simultaneously.As can be seen from the Patents and documents and materials of above-mentioned retrieval: do not see in crosslinked halogen-free flame-retardant polyolefin cable material and use the report of expansion type phosphor nitrogen based flame retardant and its cross-linking method mainly contains that high-energy radiation is crosslinked, peroxide chemical is crosslinked and silane cross-linking method three kinds, the former facility investment is high, Operation and Maintenance is complicated and safety precaution is also comparatively harsh, and is not suitable for doing the cable of larger wire diameter because its process characteristic is only suitable for doing the electric wire of less wire diameter; Peroxide chemical is cross-linked the longer curing tube that rule needs High Temperature High Pressure, and investment is large, and energy utilization rate is low, and technique is comparatively complicated, and is not suitable for the production of less wire diameter electric wire; And silane cross-linking method relates to hydrolysis reaction, the poor stability of goods, pressure high-temp resistant grade is also lower.
In recent years, applicant has invented a kind of novel uv cross-linking method (Chinese invention patent publication number: CN 1218963 and CN 1919571), and the industrialization having dropped into cross-linked wire and cable is produced.This new technology has unique advantage: the investment of required cross-linking apparatus is low, technique simple, convenient operating maintenance, energy-conserving and environment-protective, production efficiency cost that is high, product are low, high-temperature stability and good mechanical performance, simultaneously owing to adopting UV-light as irradiation source, be applicable to the photo-crosslinking electric wire product manufacturing different wire diameter.In Chinese Patent Application No. 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 under the light initiation system of free radical photo-initiation and linking agent that applicant discloses with metal hydroxides, and its product properties is excellent.But usually need the addition of 100-180% just can meet the requirements of flame retardant effect because its flame retarding efficiency is lower, add that the consistency of metal hydroxides and matrix resin is poor, therefore also bring mechanical property serious deterioration and extrude the shortcomings such as processing difficulties.In Chinese Patent Application No. 200810023192.2, applicant describes again and carries out with PE, EVA, phosphorus-nitrogen expansion type fire retardant, free radical photo-initiation and linking agent etc. insulation and the sheath material that uv cross-linking method prepares photo-crosslinking expansion type phosphor nitrogen class fire retardant polyolefin cable, fire block articles performance and good mechanical performance, oxygen index is greater than 30%, vertical combustion experiment is by UL-94V-0 level, tensile strength is greater than 12MPa, and elongation at break is greater than 350%, and volume specific resistance is greater than 2 × 10
13Ω .m, heat aging performance is excellent, and melt viscosity is low, and processing characteristics is better.Expansion type phosphor nitrogen based flame retardant is the efficient halogen-free flame retardants of a class, and when this based flame retardant is heated, due to the synergy of phosphorus and nitrogen, surface forms the foamed char of one deck densification, plays heat insulation, oxygen barrier, presses down the effect of cigarette.Relative to metal hydroxide combustion inhibitor as magnesium hydroxide, aluminium hydroxide etc., there is addition few, generally only need the addition of 30-50%, on mechanical property, the less and flame retarding efficiency advantages of higher of processing characteristics impact of polymeric matrix.But, applicant finds that the patent of above-mentioned application exists the defect of following two aspects in actual use: what no matter the first added is expansion type phosphor nitrogen based flame retardant, or metal hydroxides mineral filler, except serious deterioration except the mechanical property of polymeric matrix and processing characteristics, what cause larger negative impact is seriously hinder UV-light penetrativity in the polymeric material, cause the bottom of thicker sample (such as 1.5mm and above thickness) cannot obtain full cross-linked, have a strong impact on use properties and the range of application of fire retardant material; It two is due to the easy moisture absorption of expansion type phosphor nitrogen based flame retardant, the moisture often in use in absorbing environmental and cause electric property and the flame retardant properties degradation of material.Therefore, how to overcome the shortcoming of adding the cross-linking depth deficiency that expansion type phosphor nitrogen class halogen-free flame retardants brings, improve the penetration depth of UV-light in expandable flame retardant polymer composites and photo-initiated crosslinking efficiency, and how to solve expansion type flame retardant in use hygroscopicity problems become the key technical problem of development photo-crosslinking expansion type phosphor nitrogen class Halogen-free flame-retardant cable material.
Polymeric U photo-crosslinking mainly adopts two photoinitiators: the most normally used class is free radical photo-initiation at present, as hydrogen-capture-type light initiator benzophenone (BP) class and crack type photoinitiator benzoin dimethylether (BDK) etc., they produce free radical after absorbing UV-light and cause crosslinking reaction, but because the penetration power of UV-light is more weak, especially causing radical crosslinking reaction containing the deep layer being difficult to be penetrated into material in Packed thicker sample.But another kind of very important light trigger is cation light initiator, only has a small amount of application in coating curing field at present.
Summary of the invention
The object of the invention is to overcome the shortcoming existed in above-mentioned photo-crosslinking prior art.Contriver's novel light initiation system that surprised discovery cation light initiator and free radical photo-initiation combine in long-term electric wire development research and production practice is at light intensity 400-4000mW/cm
2the unusual effect that melting state on-line continuous ultraviolet light irradiation cross-linking 0.5-20 obtains deep-crosslinked second is carried out under the specific UV light conditions that wavelength 200-500nm and intensity of emission spectra distribution thereof and cation light initiator absorption spectrum and intensity distribution thereof match, adopt tensio-active agent to carry out surface modified pre-treatment to expansion type phosphor nitrogen class halogen-free flame retardants simultaneously, to shield the water suction group in its molecular structural formula, again in formula system with the use of grafted polyolefinic resin, the various complex art such as retardant synergist and smoke suppressor means improve the degree of depth penetrativity of UV-light in expansion type phosphor nitrogen class bittern-free flame-proof material and photo-initiated crosslinking efficiency and solve the series of key techniques problem of this kind of halogen-free flame retardants moisture absorption, low to the investment of development cross-linking apparatus, technique is simple, production efficiency is high, product cost is low, energy-conserving and environment-protective, the expansion type phosphor nitrogen class halogen-free flame-retardant polyolefin electric wire and cable novel material of Deep Ultraviolet photo-crosslinking can be reached, open up the preparation method with expansion type phosphor nitrogen class ultraviolet deep-crosslinked expandable flame retardant (referring to that expansion type phosphor nitrogen class the is fire-retardant) cable material of polyolefin (referring to cable insulation or sheath material) that is main flame retardant and insulation layer or restrictive coating.
Ultraviolet deep-crosslinked expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin cable insulation or sheath material provided by the invention, it is characterized in that using polyethylene or Grafted Polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by base-material gross weight 100 parts, add surface modification expansion type phosphor nitrogen class halogen-free flame retardants 20-50 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.1-5.0 weight part, multi-group crosslink agent 0.1-5.0 weight part, composite antioxidant 0.01-1.0 weight part, be equipped with retardant synergist 0.5-5.0 weight part, smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 parts by weight of composition form.
Ultraviolet deep-crosslinked expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin cable insulation or sheath material provided by the invention is prepared into the method for cable insulation or restrictive coating, it is characterized in that: using polyethylene or Grafted Polyethylene and/or ethylene vinyl acetate or its graft modification multipolymer as base-material, by base-material gross weight 100 parts, add surface modification expansion type phosphor nitrogen class halogen-free flame retardants 20-50 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.1-5.0 weight part, multi-group crosslink agent 0.1-5.0 weight part, composite antioxidant 0.01-1.0 weight part, be equipped with retardant synergist 0.5-5.0 weight part, after smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 weight part mix, extrude at 140-200 DEG C and be prepared into photo-crosslinking fire-resistant cable material, then on conductive cable cores, melt extrude this fire-resistant cable material coated 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 match, can adopt respectively be equipped with thermoelectron excite middle pressure mercuryarc lamp or be equipped with H type, the middle pressure microwave-excitation Non-polarized lamp of V-type that is added with the D type of ferro element and is added with gallium element is carry out melting state on-line continuous ultraviolet light irradiation 0.5-20 second to insulation layer or restrictive coating in the ultraviolet light irradiation cross-linking apparatus of light source, is cross-linked into cable insulation or restrictive coating to reach uniform depth.
Ultraviolet deep-crosslinked expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin cable insulation or sheath material provided by the invention and be prepared in the method for cable insulation or restrictive coating, described polyethylene is Low Density Polyethylene (LDPE), LLDPE (LLDPE) or high density polyethylene(HDPE) (HDPE); Described Grafted Polyethylene is glycidyl methacrylate graft polyethylene or maleic anhydride grafted polyethylene; The EVA that described ethylene vinyl acetate (EVA) is 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 expansion type phosphor nitrogen class halogen-free flame retardants refers to following one or multiple combination: 1. collect the compound of acid source source of the gas and the combination of charcoal source compound and source of the gas compound; 2. the compound of acid source source of the gas and the combination of carbon-collecting source source of the gas compound is collected; 3. collect acid source, source of the gas and charcoal and come from P-N type fire retardant in a molecule.The described compound of collection acid source source of the gas and the combination of charcoal source compound and source of the gas compound refer to:
The mixture of ammonium polyphosphate (APP) and tetramethylolmethane (PER),
The mixture of melamine phosphate (MPP) and tetramethylolmethane,
The mixture of Melamine Polyphosphate and tetramethylolmethane or
The multiple mixture of ammonium polyphosphate, tetramethylolmethane, trimeric cyanamide or melamine cyanurate (MCA).
The compound of described collection acid source source of the gas and the combination of carbon-collecting source source of the gas compound refer to the mixture of polyphosphoric acid amine and macro molecular triazine based compound.
The P-N type fire retardant that described collection acid source, source of the gas and charcoal come from one (in a molecule) refers to melamine salt of pentaerythritol phosphate compounds, as commercially available fire-retardant N P28.
The surface-modifying agent of described surface modification expansion type phosphor nitrogen class halogen-free flame retardants is organosilicon alkanes tensio-active agent or alkyl-based surfactant.Described organosilicon alkanes tensio-active agent is selected from containing hydrogen silicone oil or vinyl silicone oil; Alkyl-based surfactant is selected from undecylenic acid, stearic acid or stearylamine.The reason of the easy moisture absorption of expansion type phosphor nitrogen class halogen-free flame retardants is because containing water-absorbent group in the molecular structure of this fire retardant, by adopting suitable surface modification technology to shield this water suction group, reducing with this or eliminate the moisture absorption of expansion type phosphor nitrogen based flame retardant and improve the poor problem of itself and matrix resin consistency.
Described cation light initiator is diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt or ferrocene salt (also title iron arene salt), such as 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, 10-(4-xenyl)-ITX-10-sulphur hexafluorophosphate, cationic photoinitiator, ferrocene-4-fluoroborate or triaryl phosphofluoric acid sulfosalt etc.The action character of cation light initiator is activated the cation activity center of generation to cause coating photocuring (being namely cross-linked) reaction through ultraviolet light irradiation, and cationic photo-initiated crosslinking does not generally stop the impact of illumination or thickness of sample by sample, because cationoid reaction creates again new cation activity center while chain tra nsfer termination reaction on polymer chain, can continue to cause the crosslinking reaction strengthened in the polymeric matrix deep layer position stopping ultraviolet lighting or UV-light to arrive, that is, cationic photopolymerization is crosslinked is not dead crosslinking reaction, as long as the initial stage accepts photoirradiation, later stage, dark crosslinking reaction was carried out in the same old way smoothly.The main absorption spectrum of former three salt cation light initiator usually concentrates on and is less than 300nm wave band district, and the dominant absorption spectrum of the latter's ferrocene salt cationoid light trigger is then usual is being greater than 360nm wave band district.But current normally used middle pressure mercuryarc lamp or the emmission spectrum scope of microwave-excitation Non-polarized lamp and the dominant absorption spectrum of intensity distribution and these cation light initiators thereof and intensity distribution range Incomplete matching, thus cannot give full play to its photo-initiated crosslinking efficiency.The present invention adopts following two kinds of technical schemes to solve this " Incomplete matching " problem: the novel light initiation system that one adopts cation light initiator to match with free radical photo-initiation, effective sensitizing agent (also claiming transfer transport activator) as a kind of in normally used free radical photo-initiation benzophenone, the existence of free radical photo-initiation can improve the efficiency of cation light initiator photo-initiated crosslinking under ultraviolet light irradiation; It two is selected the ultraviolet source of proper emission wavelength region and intensity distribution thereof and the absorbing wavelength of corresponding cation light initiator and intensity distribution thereof and matches.Such as, the cation light initiator being less than 300nm is concentrated on to absorbing wavelength and just can adopt H type microwave-excitation Non-polarized lamp, because its major absorbance peak concentrates between 200-300nm, the cation light initiator being greater than 360nm is concentrated on to absorbing wavelength and then can adopt the D type that with the addition of metallic iron element or the V-type microwave-excitation Non-polarized lamp that with the addition of gallium element respectively.Add the ultraviolet ray intensity that ferro element can make 320-400nm place export in mercury lamp obviously to increase, when the ultraviolet light intensity that add gallium element the output of 405-440nm place then can be made very high.Emmission spectrum and the intensity distribution range thereof of ultraviolet lamp can be changed by interpolation metallic elements of ferrum or gallium, to coordinate absorption spectrum and the intensity distribution range thereof of cation light initiator, cation light initiator can be made during illumination to absorb more UV energy, strengthen the crosslinked ability of its deep layer and improve its photo-initiated crosslinking efficiency.
Described free radical photo-initiation is one or more combinations in benzoin dimethylether (BDK), Dialkoxy acetophenones, Oxoxanthone, anthraquinone, Fluorenone or benzophenone (BP) and 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 ether (PETAE), tetramethylolmethane four allyl ether or triethylene glycol methacrylate (TEGMA), or its mixture.
Described composite antioxidant is by two or more phenols, phosphorous acid esters, phosphoric acid ester or form containing sulphur ester antioxidant, and composite antioxidant is preferably phenolic antioxidant and phosphorous acid esters or combines containing thioesters class; Described phenolic antioxidant comprises 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, 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; Described containing sulphur ester antioxidant, comprise Tyox B (DLTP), thio-2 acid bay octadecyl ester (LSTP) or thio-2 acid two (13) ester (DTDTP); You Yisi [methylene radical-3-(3 ', 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 (irgasfos 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 thereof and/or silicoorganic compound, as sodium stearate, Magnesium Stearate, Zinic stearas, calcium stearate, polydimethylsiloxane, silicone resin or hydroxy silicon oil.
Described specific UV light source is that thermoelectron excites the large class medium pressure mercury lamp of mercuryarc lamp and microwave-excitation Non-polarized lamp two, and wherein 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.Emmission spectrum and the intensity distribution range thereof of ultraviolet lamp can be changed by interpolation metallic elements of ferrum or gallium, to coordinate absorption spectrum and the intensity distribution range thereof of cation light initiator, cation light initiator can be made during illumination to absorb more UV energy, strengthen the crosslinked ability of its deep layer and improve photo-crosslinking efficiency.
The insulation of ultraviolet deep-crosslinked expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin cable provided by the invention or the feature of sheath material and insulation layer or restrictive coating preparation method be adopt the novel light initiation system that combines with free radical photo-initiation of cation light initiator and coordinates specific UV light source selected by cation light initiator to carry out ultraviolet light irradiation cross-linking and in bittern-free flame-proof material formula system with the use of various complex art means such as the expansion type phosphor nitrogen combustion inhibitors of grafted polyolefinic resin and surface modification to improve the poor and photo-initiated crosslinking efficiency of the deep layer penetrativity of UV-light in expansion type phosphor nitrogen class Halogen-free flame-retardant cable material and to solve the expansion type flame retardant in use key technical problem such as the easy moisture absorption, there is provided a kind of crosslinking process simple, facility investment is low, energy-conserving and environment-protective, production efficiency is high, the measured novel production method of product cost low-quality manufactures the expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin insulated wire cable of ultraviolet deep homogeneous cross-link.
Compared with original photo-crosslinking expansion type phosphor nitrogen class halogen-free flame-retardant cable technology, owing to present invention employs the novel light initiation system that cation light initiator and free radical photo-initiation combine, except free radical photo-initiated crosslinking, the cation activity center of also causing by the cation light initiator in system completes crosslinking reaction, and this cationic crosslinked reaction is not generally by the impact of thickness of sample, because cationoid reaction creates again new cation activity center while chain tra nsfer termination reaction on polymer chain, can continue to cause the crosslinking reaction (also claiming dark reaction) strengthened in the polymeric matrix deep layer position stopping ultraviolet lighting or UV-light to arrive.Meanwhile, the free radical photo-initiation used in system is the effective sensitizing agent of cation light initiator (also claiming transfer transport activator) normally, and the UV-light that can strengthen cation light initiator further causes cross-linking efficiency.Before so just overcoming in Chinese Patent Application No. 200810023192.2 simple use free radical photo-initiation must absorb UV-light after could cause the shortcoming of crosslinking reaction, thus efficiently solve UV-light penetration power more weak being difficult to and be penetrated into the difficult problem containing expansion type phosphor nitrogen class bittern-free flame-proof material deep layer initiation crosslinking reaction.
Compared with the ultraviolet source used in original crosslinking halogen-free flame-retardant cable technology, ultraviolet light irradiation cross-linking apparatus of the present invention has selected light intensity 400-4000mW/cm
2, the specific UV light source that wavelength 200-500nm and intensity distribution thereof and cationic photopolymerization initiator system absorption spectrum and intensity distribution range thereof match, as thermoelectron excites the H type lamp of middle pressure mercuryarc lamp or microwave-excitation Non-polarized lamp, be added with the D type lamp of ferro element or be added with the V-type lamp of gallium element, more UV energy is absorbed to make cationic photopolymerization initiator system, at utmost improve its ability that light-initiated efficiency and deep layer are cross-linked in halogen-free anti-flaming polyolefin material, thus make the even photo-crosslinking degree of depth of expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin material bring up to more than 3.0mm from original less than 1.5mm.Simultaneously shield water-absorbent group in its molecular structure owing to having carried out effective finishing to expansion type phosphor nitrogen class halogen-free flame retardants, the moisture absorption of this expansion type phosphor nitrogen class bittern-free flame-proof material is made to obtain very big improvement, also enhance the consistency of expansion type phosphor nitrogen class halogen-free flame retardants and polyolefine material simultaneously, significantly improve the mechanical property of material, flame retardant properties and heat aging performance.
, chemically crosslinked crosslinked with existing traditional high-energy radiation is prepared halogen-free anti-flaming polyolefin cable material with crosslinked with silicane technology and is compared, ultraviolet deep-crosslinked expansion type phosphor nitrogen class halogen-free anti-flaming polyolefin cable insulation of the present invention and sheath material and preparation method thereof have unique technical superiority: the investment of required cross-linking apparatus is low, technique simple, convenient operating maintenance, and energy-conserving and environment-protective, production efficiency cost inferior quality that is high, product are good; Finishing has been carried out to it owing to have employed expansion type phosphor nitrogen class halogen-free flame retardants simultaneously, substantially improve the moisture absorption of fire retardant and the dispersiveness in matrix resin and the consistency with matrix resin, the significant increase flame retardant properties of material product, mechanics electric property, processing characteristics and heat aging property.
Embodiment
The present invention's the following example and comparative example make concrete detailed description further to the present invention, but scope is not limited to the following example.
Embodiment 1
First finishing is carried out to the present embodiment expansion type phosphor nitrogen based flame retardant: stirred in high-speed mixer high speed respectively by APP and PER and be warming up to 100 DEG C, the stearic acid first adding a part of alcohol dilution stirs 15 minutes, the stearic acid adding the alcohol dilution of remaining part subsequently again carries out several minutes secondary stirring and is coated with the coated integrity of raising filling surface, and it is stand-by that oven dry is carried out in the agent of last effects on surface modified flame-retardant.Take LLDPE 80 parts by weight, glycidyl methacrylate graft polyethylene 8 parts, maleic anhydride grafted polyethylene 12 parts, stearic acid modified APP 35 parts, stearic acid modified PER 10 parts, 4,4 '-dimethyl diphenyl iodine phosphoric acid salt 2.5 parts, 4-chlorobenzophenone 2 parts, TMPTA 1.5 parts, antioxidant 300 0.3 part, DLTP 0.1 part, zinc borate 4 parts, Ammonium Heptamolybdate 2 parts, hydroxy silicon oil 1.5 parts; Each material component after mixing, at 180 DEG C of extruding pelletizations; Then this flame-proof material melt extruding coated 2.8mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with H type microwave-excitation Non-polarized lamp, crosslinking time is 5 seconds.Experimental result shows: the tensile strength of UV-light deep layer crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by the present embodiment is 15.2MPa, elongation at break 580%, oxygen index 33%, vertical combustion experiment is by UL-94V-0 level, heat extends 80%, by the thermal ageing test of 158 DEG C × 168h, volume specific resistance is 8.9 × 10
14Ω .m, volume specific resistance 4.3 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Comparative example 1
Do not adopt cation light initiator 4,4 '-dimethyl diphenyl iodine phosphoric acid salt but simultaneous test under keeping light trigger parts by weight and the constant situation of other conditions: to the method for expansion type phosphor nitrogen based flame retardant APP and PER stearic acid surface-modified as described in Example 1; Take LLDPE 80 parts by weight, glycidyl methacrylate graft polyethylene 8 parts, maleic anhydride grafted polyethylene 12 parts, stearic acid modified APP 35 parts, stearic acid modified PER 10 parts, 4-chlorobenzophenone 4.5 parts, TMPTA 1.5 parts, antioxidant 300 0.3 part, DLTP 0.1 part, zinc borate 4 parts, Ammonium Heptamolybdate 2 parts, hydroxy silicon oil 1.5 parts; Each material component after mixing, at 180 DEG C of extruding pelletizations; Then this flame-proof material melt extruding coated 2.8mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with H type microwave-excitation Non-polarized lamp, crosslinking time is 5 seconds.Experimental result shows: the tensile strength of ultraviolet crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by this comparative example is 13.1MPa, elongation at break 670%, oxygen index 32%, vertical combustion experiment is by UL-94V-0 level, cannot be extended the thermal ageing test of experiment and 158 DEG C × 168h by heat, volume specific resistance is 6.7 × 10
14Ω .m, volume specific resistance 3.3 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Embodiment 2
Finishing is carried out to the present embodiment expansion type phosphor nitrogen based flame retardant: stirred in high-speed mixer high speed respectively by MPP and PER and be warming up to 120 DEG C, the vinyl silicone oil adding a part of alcohol dilution stirs 15 minutes, the vinyl silicone oil adding the alcohol dilution of remaining part afterwards again carries out several minutes secondaries and is coated with the coated integrity of raising filling surface, and sampling drying is stand-by.Take LDPE 70 parts by weight, glycidyl methacrylate graft EVA 10 parts, maleic anhydride grafted polyethylene 20 parts, the MPP 30 parts of vinyl silicone oil modification, the PER 10 parts of modification, 10-(4-xenyl)-ITX-10-sulphur hexafluorophosphate 2 parts, 4,4 ' dichloro benzophenone 2.5 parts, TAIC 3 parts, antioxidant 1010 0.1 part, DTDTP 0.5 part, phosphorous acid ester 3 parts, molybdenum sesquioxide 1 part, Magnesium Stearate 2.5 parts; At 165 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 2.0mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with H type microwave-excitation Non-polarized lamp, crosslinking time is 6 seconds.Experimental result shows: the tensile strength of UV-light deep layer crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by the present embodiment is 16.6MPa, elongation at break 580%, oxygen index 32%, vertical combustion experiment is by UL-94V-0 level, hot unit elongation 75%, by the thermal ageing test of 158 DEG C × 168h, volume specific resistance is 8.2 × 10
14Ω .m, volume specific resistance 4.8 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Comparative example 2
Expansion type phosphor nitrogen class halogen-free flame retardants in this comparative example is not by the simultaneous test of vinyl silicone oil finishing but other condition remains unchanged in situation: take LDPE 70 parts by weight, glycidyl methacrylate graft EVA 10 parts, maleic anhydride grafted polyethylene 20 parts, the MPP of non-finishing 30 parts, the PER of non-finishing 10 parts, 10-(4-xenyl)-ITX-10-sulphur hexafluorophosphate 2 parts, 4, 4 ' dichloro benzophenone 2.5 parts, TAIC 3 parts, antioxidant 1010 0.1 part, DTDTP 0.5 part, phosphorous acid ester 3 parts, molybdenum sesquioxide 1 part, Magnesium Stearate 2.5 parts, at 165 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 2.0mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with H type microwave-excitation Non-polarized lamp, crosslinking time is 6 seconds.Experimental result shows: the tensile strength of ultraviolet crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by this comparative example is 15.2MPa, elongation at break 430%, oxygen index 32%, vertical combustion experiment is by UL-94V-0 level, hot unit elongation 75%, by the thermal ageing test of 158 DEG C × 168h, volume specific resistance is 8.2 × 10
14Ω .m, volume specific resistance < 10 after immersion 70 DEG C × 168h
10Ω .m.
Embodiment 3
Finishing is carried out to the present embodiment expansion type phosphor nitrogen based flame retardant: APP and macro molecular triazine based compound are warming up to 140 DEG C in the stirring of high-speed mixer high speed, the stearylamine adding a part of alcohol dilution stirs 15 minutes, the stearylamine adding the alcohol dilution of remainder afterwards again carries out several minutes secondaries and is coated with the coated integrity of raising filling surface, and sampling drying is stand-by.Take EVA 85 parts by weight, glycidyl methacrylate graft EVA 10 parts, acid amide-grafted ethylene vinyl acetate copolymer 5 parts, the APP 25 parts of stearylamine modification, stearylamine modified macromer triazine based compound 10 parts, cationic photoinitiator 2.0 parts, dodecyl benzophenone 4 parts, TAC 2.0 parts, antioxidant 1010 0.1 part, DLTP 0.2 part, silicotungstic acid 2.5 parts, molybdenum sesquioxide 3 parts, hydroxy silicon oil 1.5 parts; At 140 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 3.0mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with D type microwave-excitation Non-polarized lamp, crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of UV-light deep layer crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by the present embodiment is 16.2MPa, elongation at break 630%, oxygen index 30%, vertical combustion experiment is by UL-94V-0 level, hot unit elongation 85%, by the thermal ageing test of 135 DEG C × 168h, volume specific resistance is 8.5 × 10
14Ω .m, volume specific resistance 4.5 × 1014 Ω .m after immersion 70 DEG C × 168h.
Comparative example 3
Common middle pressure mercuryarc lamp is adopted to substitute the contrast experiment of D type microwave-excitation Non-polarized lamp and crosslinking time and other condition remain unchanged in situation: the stearylamine finishing of this comparative example expansion type phosphor nitrogen based flame retardant APP and macro molecular triazine based compound as described in Example 3; Take EVA 85 parts by weight, glycidyl methacrylate graft EVA 10 parts, acid amide-grafted ethylene vinyl acetate copolymer 5 parts, the APP 25 parts of stearylamine modification, macro molecular triazine based compound 10 parts, cationic photoinitiator 2.0 parts, dodecyl benzophenone 4 parts, TAC2.0 part, antioxidant 1010 0.1 part, DLTP 0.2 part, silicotungstic acid 2.5 parts, molybdenum sesquioxide 3 parts, hydroxy silicon oil 1.5 parts; At 140 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 3.0mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with common middle pressure mercuryarc lamp, crosslinking time is 4.5 seconds.Experimental result shows: the tensile strength of ultraviolet crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by this comparative example is 12.2MPa, elongation at break 680%, oxygen index 30%, vertical combustion experiment is by UL-94V-0 level, cannot by the thermal ageing test of hot elongation test and 135 DEG C × 168h, volume specific resistance is 7.0 × 10
14Ω .m, volume specific resistance 1.5 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Embodiment 4
Finishing is carried out to the present embodiment expansion type phosphor nitrogen based flame retardant: stirred in high-speed mixer high speed by NP28 and be warming up to 120 DEG C, the undecylenic acid adding a part of alcohol dilution stirs 15 minutes, the undecylenic acid adding the alcohol dilution of remainder afterwards again carries out several minutes secondaries and is coated with the coated integrity of raising filling surface, sampling drying.Take LDPE 80 parts by weight, glycidyl methacrylate graft LDPE 5 parts, maleic anhydride graft LDPE 15 parts, the NP28 of undecylenic acid modification 35 parts, ferrocene-4-fluoroborate 2.0 parts, dodecyl benzophenone 3 parts, TMPTA 2 parts, antioxidant 1010 0.25 part, DTDTP 0.15 part, zinc silicate 1.5 parts, ammonium octamolybdate 2 parts, dimethyl silicone oil 2.5 parts; At 160 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 2.5mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with V-type microwave-excitation Non-polarized lamp, crosslinking time is 0.5 second.Experimental result shows: the tensile strength of UV-light deep layer crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by the present embodiment is 17.2MPa, elongation at break 510%, oxygen index 31%, vertical combustion experiment is by UL-94V-0 level, hot unit elongation 50%, by the thermal ageing test of 158 DEG C × 168h, volume specific resistance is 9.2 × 10
14Ω .m, volume specific resistance 5.6 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Comparative example 4
Common middle pressure mercuryarc lamp is adopted to substitute V-type microwave-excitation Non-polarized lamp and crosslinking time is increased to contrast experiment and other condition remains unchanged in situation 15 seconds: to carry out undecylenic acid finishing as described in Example 4 to this routine expansion type phosphor nitrogen based flame retardant NP28; LDPE 80 parts will be taken by weight, glycidyl methacrylate graft LDPE 5 parts, maleic anhydride graft LDPE 15 parts, NP2835 part of undecylenic acid modification, ferrocene-4-fluoroborate 2.0 parts, dodecyl benzophenone 3 parts, TMPTA 2 parts, antioxidant 1010 0.25 part, DTDTP 0.15 part, zinc silicate 1.5 parts, ammonium octamolybdate 2 parts, dimethyl silicone oil 2.5 parts; At 160 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 2.5mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with common middle pressure mercuryarc lamp, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of ultraviolet crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by this comparative example is 13.5MPa, elongation at break 590%, oxygen index 30%, vertical combustion experiment is by UL-94V-0 level, cannot by the thermal ageing test of hot elongation test and 135 DEG C × 168h, volume specific resistance is 6.1 × 10
14Ω .m, volume specific resistance 1.3 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Embodiment 5
Finishing is carried out to the present embodiment expansion type phosphor nitrogen based flame retardant: APP and macro molecular triazine based compound are warming up to 130 DEG C in the stirring of high-speed mixer high speed, the stearylamine adding a part of alcohol dilution stirs 15 minutes, the stearylamine adding the alcohol dilution of remainder afterwards again carries out several minutes secondaries and is coated with the coated integrity of raising filling surface, and sampling drying is stand-by.Take EVA (VA content 18%) 70 parts by weight, glycidyl methacrylate graft EVA 15 parts, maleic anhydride grafted ethene vinyl acetate copolymer 15 parts, stearylamine modification APP 30 parts, stearylamine modified macromer triazine based compound 10 parts, triaryl phosphofluoric acid sulfosalt 2.0 parts, BP 2.5 parts, TAIC 2.5 parts, antioxidant 1010 0.15 part, DLTP 0.15 part, phosphoric acid ester 2 parts, molybdenum sesquioxide 2 parts, hydroxy silicon oil 2.5 parts; At 160 DEG C of extruding pelletizations after each material component mixes, then this flame-proof material melt extruding coated 2.0mm thick on conductive cable cores becomes insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with common medium pressure mercury lamp, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of UV-light deep layer crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by the present embodiment is 15.5MPa, elongation at break 590%, oxygen index 32%, vertical combustion experiment is by UL-94V-0 level, hot unit elongation 45%, by the thermal ageing test of 135 DEG C × 168h, volume specific resistance is 8.8 × 10
14Ω .m, volume specific resistance 5.1 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Comparative example 5
Do not adopt cation light initiator triaryl phosphofluoric acid sulfosalt but keep light trigger parts by weight and the simultaneous test in the constant situation of other conditions: as embodiment 5 couples of expansion type phosphor nitrogen based flame retardant APP and macro molecular triazine based compound carry out stearylamine finishing; Take EVA (VA content 18%) 70 parts by weight, glycidyl methacrylate graft EVA 15 parts, maleic anhydride grafted ethene vinyl acetate copolymer 15 parts, stearylamine modification APP 30 parts, stearylamine modified macromer triazine based compound 10 parts, BP 4.5 parts, TAIC 2.5 parts, antioxidant 1010 0.15 part, DLTP 0.15 part, phosphoric acid ester 2 parts, molybdenum sesquioxide 2 parts, hydroxy silicon oil 2.5 parts.At 160 DEG C of extruding pelletizations after each material component mixes, then on conductive cable cores, melt extrude this thick flame-proof material of coated 2.0mm become insulation layer or restrictive coating, insulation layer or restrictive coating are carried out to the ultraviolet light irradiation cross-linking of melting state on-line continuous immediately in the ultraviolet light irradiation cross-linking apparatus being light source with common medium pressure mercury lamp, crosslinking time is 15 seconds.Experimental result shows: the tensile strength of ultraviolet crosslinked expansion type P-N type fire retardant polyolefin cable material prepared by this comparative example is 11.5MPa, elongation at break 670%, oxygen index 31%, vertical combustion experiment is by UL-94V-0 level, cannot hot elongation test and by the thermal ageing test of 135 DEG C × 168h, volume specific resistance is 4.8 × 10
14Ω .m, volume specific resistance 1.1 × 10 after immersion 70 DEG C × 168h
14Ω .m.
Claims (7)
1. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation or a sheath material, is characterized in that:
Polyethylene, the compound of modified by maleic acid anhydride graft polyethylene and ethylene copolymers and glycidyl methacrylate graft multipolymer or ethylene vinyl acetate copolymer, the compound of ethylene vinyl acetate graft modification multipolymer and glycidyl methacrylate graft multipolymer is base-material, by base-material gross weight 100 parts, add surface modification expansion type phosphor nitrogen class halogen-free flame retardants 20-50 weight part, cation light initiator 0.5-5.0 weight part, free radical photo-initiation 0.1-5.0 weight part, multi-group crosslink agent 0.1-5.0 weight part, composite antioxidant 0.01-1.0 weight part, be equipped with retardant synergist 0.5-5.0 weight part, smoke suppressor 0.5-10.0 weight part and processing aid 0.5-5.0 parts by weight of composition form, described polyethylene is Low Density Polyethylene, LLDPE or high density polyethylene(HDPE), described ethylene vinyl acetate copolymer is the EVA of 14-80%VA content, described glycidyl methacrylate graft multipolymer is glycidyl methacrylate graft polyethylene and ethylene copolymers or glycidyl methacrylate graft ethylene vinyl acetate copolymer, described ethylene vinyl acetate graft modification multipolymer is modified by maleic acid anhydride graft ethylene vinyl acetate copolymer or acid amide-grafted modified ethylene vinyl acetate vinyl ester copolymers,
Described surface modification expansion type phosphor nitrogen class halogen-free flame retardants is one or more combinations of following surface modification; 1. collect the compound of acid source source of the gas and the combination of charcoal source compound and source of the gas compound, 2. the compound of collection acid source source of the gas and the combination of carbon-collecting source source of the gas compound, 3. collect acid source, source of the gas and charcoal and come from P-N type fire retardant in a molecule;
The surface-modifying agent of described surface modification expansion type phosphor nitrogen class halogen-free flame retardants is organosilicon alkanes tensio-active agent, undecylenic acid or stearylamine;
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 acetophenones, Oxoxanthone, anthraquinone, Fluorenone or benzophenone and derivative thereof;
Described multi-group crosslink agent is triallyl cyanurate, cyamelide triallyl, trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris allyl ether, tetramethylolmethane three allyl ether, tetramethylolmethane four allyl ether or triethylene glycol methacrylate, or its mixture;
Described composite antioxidant is by two or more phenols, phosphorous acid esters, phosphoric acid ester or forms containing sulphur ester antioxidant, 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; Described is Tyox B, thio-2 acid bay octadecyl ester or thio-2 acid two (13) ester containing sulphur ester antioxidant;
Described retardant synergist is zinc borate, ferrocene, polynite, silicon-dioxide, 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 thereof or silicoorganic compound.
2. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation according to claim 1 or sheath material, described zinc borate is superfine zinc borate.
3. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation according to claim 1 or sheath material, described silicon-dioxide is aerosil.
4. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation according to claim 1 or sheath material, described organosilicon compound is silica gel.
5. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation according to claim 1 or sheath material, is characterized in that: the compound of described collection acid source source of the gas and being combined as of source of the gas compound:
The mixture of ammonium polyphosphate and tetramethylolmethane,
The mixture of melamine phosphate and tetramethylolmethane,
The mixture of Melamine Polyphosphate and tetramethylolmethane or
The multiple mixture of ammonium polyphosphate, tetramethylolmethane, trimeric cyanamide and melamine cyanurate;
The compound of described collection acid source source of the gas and the mixture being combined as ammonium polyphosphate and macro molecular triazine based compound of carbon-collecting source source of the gas compound;
The P-N type fire retardant that described collection acid source, source of the gas and charcoal come from a molecule refers to melamine salt of pentaerythritol phosphate compounds;
Described organosilane tensio-active agent is containing hydrogen silicone oil or vinyl silicone oil;
Described cation light initiator is 4,4 '-dimethyl diphenyl iodine phosphoric acid salt, two dodecylbenzene hexafluoroarsenate salt compounded of iodine, 10-(4-xenyl)-ITX-10-sulphur hexafluorophosphate, phosphofluoric acid triaryl sulfonium salts, triphenyl hexafluoro-antimonic acid sulfosalt, ferrocene-4-fluoroborate or cationic photoinitiator;
Described composite antioxidant is with phenolic antioxidant and phosphorous acid esters or contains the composite composite antioxidant of thioesters class, or with four [methylene radical-3-(3 ', 5 '-di-tert-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;
Described processing aid is sodium stearate, Magnesium Stearate, Zinic stearas, calcium stearate, polydimethylsiloxane, silicone resin or hydroxy silicon oil.
6. be prepared into the method for cable insulation or restrictive coating according to the arbitrary described ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation of claim 1 or 5 or sheath material, it is characterized in that:
The compound of polyethylene, modified by maleic acid anhydride graft polyethylene and ethylene copolymers and glycidyl methacrylate graft multipolymer
Or ethylene vinyl acetate copolymer, the compound of ethylene vinyl acetate graft modification multipolymer and glycidyl methacrylate graft multipolymer is base-material, by base-material gross weight 100 parts, add surface modification expansion type phosphor nitrogen combustion inhibitor 20-50 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 0.1-5.0 weight part, composite antioxidant 0.01-1.0 weight part, be equipped with 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, extrude at 140-200 DEG C and be prepared into photo-crosslinking expandable flame retardant CABLE MATERIALS, then on conductive cable cores, melt extrude this fire-resistant cable material coated 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 match, adopt and be equipped with thermoelectron and excite middle pressure mercuryarc lamp or the V-type microwave-excitation Non-polarized lamp that H type is housed, is added with the D type of ferro element or is added with gallium element is carry out melting state on-line continuous ultraviolet light irradiation 0.5-20 second to insulation layer or restrictive coating in the ultraviolet light irradiation cross-linking apparatus of specific light source respectively, be cross-linked into cable insulation or restrictive coating to reach uniform depth,
The surface-modifying agent of described surface modification expansion type phosphor nitrogen class halogen-free flame retardants is containing hydrogen silicone oil, vinyl silicone oil, undecylenic acid or stearylamine;
Described composite antioxidant is four [methylene radical-3-(3 ', 5 '-di-tert-butyl-4 '-hydroxy phenyl) propionic acid] cooperation of pentaerythritol ester and triphenyl phosphite, tricresyl phosphite (2,4-di-tert-butyl phenyl) ester or Tyox B.
7. ultraviolet deep-crosslinked expansion type phosphor nitrogen class flame-retardant polyolefin cable insulation according to claim 6 or sheath material are prepared into the method for cable insulation or restrictive coating, it is characterized in that, being combined as of the compound of the gas collection source acid source of described surface modification expansion type phosphor nitrogen class halogen-free flame retardants and charcoal source compound and source of the gas compound:
The mixture of ammonium polyphosphate and tetramethylolmethane,
The mixture of melamine phosphate and tetramethylolmethane,
The mixture of Melamine Polyphosphate and tetramethylolmethane or
The multiple mixture of ammonium polyphosphate, tetramethylolmethane, trimeric cyanamide or melamine cyanurate;
The compound of described collection acid source source of the gas and the mixture being combined as ammonium polyphosphate and macro molecular triazine based compound of carbon-collecting source source of the gas compound;
Described acid source, source of the gas and the charcoal of integrating comes from P-N type fire retardant in a molecule as melamine salt of pentaerythritol phosphate compounds;
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 cationic photoinitiator;
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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Effective date of registration: 20170516 Address after: 154000 Dongfeng hi tech Industrial Development Zone, Jiamusi, Heilongjiang Patentee after: Heilungkiang Ming Xiang Science and Technology Ltd. Address before: 154004 Jiamusi city Heilongjiang Woerde Road No. 3 Co-patentee before: Muyang Youwei New Material Co., Ltd. Patentee before: Honglongjiang Orient Science & Technology Co., Ltd. |