CN102432934B - Low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve and preparation method and application thereof - Google Patents
Low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve and a preparation method and application thereof. The low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve contains 85 to 95 parts of polyolefin resin, 5 to 15 parts of maleic anhydride copolymerization modified ethylene-vinyl acetate copolymer, 30 to 70 parts of nitrogen phosphorus series expanded halogen-free flame retardant, 0 to 16 parts of expansible graphite, 1 to 3 parts of lubricating agent, 0.5 to 2.5 parts of antioxidant, 1 to 2.5 parts of sensitizer and 5 to 8 parts of black master batch. The preparation method comprises the following steps of: mixing the raw materials uniformly, extruding the mixed raw materials at the temperature of between 100 and 160 DEG C by using a double-screw extruder, and performing wire drawing, air cooling and granulation; pressing the granules into a mold shrinkage sleeve, and performing irradiation, wherein the irradiation dose is 8 to 12Mrad; and expanding and drawing the irradiated and cross-linked mold shrinkage sleeve at the temperature of between 140 and 160 DEG C, cooling and setting, and thus obtaining the low-smoke halogen-free flame-retardant mold shrinkage sleeve. The preparation method is simple; and the obtained mold shrinkage sleeve has excellent flame-retardant performance, low smoke generating quantity and good mechanical property, electrical insulating property and heat resistance.
Description
Technical field
The present invention the present invention relates to a kind of main fire-retardant mould contracting cover take ethylene-vinyl acetate copolymer as matrix resin, particularly a kind of low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve and preparation method thereof and application.
Background technology
Mould contracting cover multiplex in the cable terminal end junction, cable openings and bifurcated junction; good stress relieving, sealing and mechanical protection is provided; be divided into T shape bifurcated, 45 ° of bifurcateds, 30 ° of bifurcateds, Y shape bifurcated equal-specification, in the design that is widely used in Aeronautics and Astronautics and the electric equipment of navigation and the assembling.The early stage take-up strap that adopts coats processing, easily comes off, and is not attractive in appearance, poor reliability.The appearance of mould contracting cover has well solved the problems referred to above.Early stage mould contracting cover mostly is the Halogen system, and market mostly is external product monopolization, headed by chatting about so that the U.S. is auspicious again.Afterwards by linking up with three boat manufacturing enterprises, and many decree rules about halogen-free environmental are put into effect in succession in the international environment, and a lot of three boat manufacturing enterprises have proposed the requirement of pyrocondensation product low smoke and zero halogen, the environmental protection of low evil.Domestic and international commercially available halogen-free flameproof pattern contracting cover product adds metal hydroxides and phosphor-nitrogen expansion type combustion inhibitor more at present.Phosphor-nitrogen expansion type combustion inhibitor forms porous foam charcoal layer by the synergy performance flame retardant effect of carbon source, acid source, source of the gas on the system surface, plays the effect of anti-flaming thermal-insulation.Expansible black lead places high temperature lower time, interlayer intercalation thing to be subjected to the rapidly vaporization of high heat, and the gas of formation will produce the huge power that supports to graphite flake layer, and expansible black lead is expanded, and form thermofin, and expansion multiple can be up to hundreds of to thousands of.Therefore, people attempt preparing fire retardant material take red phosphorus and expansible black lead as raw material.But the fire retardant material that has existed at present, Shortcomings part still, for example: publication number is the fire retardant material that national inventing patent application that CN 101486814A, name are called " preparation method of low-smoke halogen-free non-nitrogen flame-retardant heat-shrinkable material sleeve pipe and sleeve pipe " discloses a kind of low-smoke halogen-free non-nitrogen, flame-retardant composition comprises phosphorus nitrogen expansion type combustion inhibitor and microcapsule red phosphorus, fire-retardant rank is FV-1, flame retardant effect is not satisfactory, and the simultaneously existence meeting of red phosphorus impacts environment.Publication number is that the national inventing patent file that CN101012326A, name are called " a kind of halogen-free flame-proof cable sheath material " discloses a kind of halogen-free flame-proof cable sheath material, with 10 parts of expansible black leads, 90 parts of magnesium hydroxides, 2～5 parts of organo montmorillonite cooperative flame retardant polyolefine, the fracture of composite materials elongation is less than 280%, although wherein use in a large number magnesium hydroxide to play to a certain extent but the effect of cigarette and improvement system drippage, also significantly reduced the mechanical property of material simultaneously.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve with not enough.
Another object of the present invention is to provide the preparation method of described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve.
A further object of the present invention is to provide the application of described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve.
Purpose of the present invention is achieved through the following technical solutions: a kind of low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve comprises following composition by mass parts:
Described polyolefin resin is preferably at least a in ethylene-vinyl acetate copolymer (EVA), linear low density polyethylene (LLDPE) or the terpolymer EP rubber (EPDM);
The mass content that described ethylene-vinyl acetate copolymer is preferably vinyl-acetic ester is 14～28%, melt index is the ethylene-vinyl acetate copolymer of 3.5～4.5g/10min (ASTM D1238);
It is 2g/10min (ASTM D1238) that described linear low density polyethylene is preferably melt index, and density is 0.918g/cm
3The linear low density polyethylene of (ASTM D792);
It is 50～65% that described terpolymer EP rubber is preferably the ethene mass content, and mooney viscosity ML (1+4) (125 ℃) is the terpolymer EP rubber of 38～52MU; More preferably Jilin Petrochemical EPDM J-4045 terpolymer EP rubber;
It is quality percentage composition 1.0～1.2% that the ethylene-vinyl acetate copolymer of described maleic anhydride modification by copolymerization (EVA-g-MAH) is preferably percentage of grafting, and melt index is the ethylene-vinyl acetate copolymer of the maleic anhydride modification by copolymerization of 1.1～2.0g/10min; More preferably percentage of grafting is quality percentage composition 1.2%, and melt index is the ethylene-vinyl acetate copolymer of the maleic anhydride modification by copolymerization of 1.1g/10min;
The consumption of described nitrogen phosphorus series expansion type halogen-free flame retardants is 34～67 mass parts more preferably;
Described nitrogen phosphorus series expansion type halogen-free flame retardants is one or both among phosphorus nitrogen expansion type combustion inhibitor A or the phosphorus nitrogen expansion type combustion inhibitor B;
The phosphorus content of described phosphorus nitrogen expansion type combustion inhibitor A is 16～20%, nitrogen content is 19～23%, 50%D is that 5.0um (represents that half particle diameter is greater than 5.0 μ m, half is less than 5.0 μ m), 90%D is 11.0 μ m (representing that 90% particle diameter is less than 11.0 μ m), and decomposition temperature is greater than 270 ℃; Be preferably the FP-2200 nitrogen phosphorus series expansion type halogen-free flame retardants that Asahi Denka Co., Ltd. produces;
The phosphorus content of described phosphorus nitrogen expansion type combustion inhibitor B is 22～24%, and nitrogen content is 20～22%, the about 10um of median size, and decomposition temperature is greater than 260 ℃; Be preferably the EPFR-100D phosphorous-nitrogen system bittern-free fire retardant that general match furan (Qingyuan City) phosphorus chemistry company limited produces;
It is that 200～400 orders, expansion multiplying power are that 150～200ml/g, carbon content are the expansible black lead of mass percent 90～99.9% that described expansible black lead is preferably median size; More preferably 400 orders, expansion multiplying power are that 150ml/g, carbon content are the expansible black lead of mass percent 90～99.9%;
Described lubricant is preferably at least a in Zinic stearas (ZnSt), Magnesium Stearate (MgSt) or the polyethylene wax;
Described antioxidant is preferably hindered phenol primary antioxidant and the efficient auxiliary antioxidant of thioether 1: 1 in mass ratio～4 proportionings and gets;
Preferred four [the β-(3 of described hindered phenol primary antioxidant, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] in pentaerythritol ester (antioxidant 1010) or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid (antioxidant 1076) one or both;
The efficient auxiliary antioxidant of described thioether is preferably one or both in Tyox B (DLTP) or thio-2 acid two (18) ester (DSTP);
Described sensitizing agent is preferably at least a in Viscoat 295 (TMPTA), tetramethylol methane tetraacrylate (PETEA) or the triallyl isocyanate (TAIC);
Described black agglomerate is preferably the black agglomerate of BLACK II (the female Co., Ltd., Factory of Guangzhou magnificent look far away);
The preparation method of described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve comprises the steps:
(1) ethylene-vinyl acetate copolymer, 30～70 mass parts nitrogen phosphorus series expansion type halogen-free flame retardantss, 0～16 mass parts expansible black lead, 1～3 mass parts lubricant, 0.5～2.5 mass parts antioxidant, 1～2.5 mass parts sensitizing agent and 5～8 mass parts black agglomerates with 85～95 mass parts polyolefin resines, 5～15 mass parts maleic anhydride modifications by copolymerization pass through stirring and evenly mixing, temperature of charge is controlled within 80 ℃ in the whipping process, obtains mixture;
(2) with mixture with twin screw extruder in 100～160 ℃ extrude, wire drawing, air-cooled, pelletizing;
(3) the pellet pressure injection after the above-mentioned pelletizing is become mould contracting cover;
(4) the mould contracting cover that step (3) is obtained carries out irradiation, and irradiation dose is 8～12Mrad;
(5) again the contracting of the mould behind the cross-linking radiation is placed in 140～160 ℃ of expansion stretchings, cooling and shaping, obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve.
Temperature of charge described in the step (1) preferably is controlled at 70～80 ℃;
Stirring described in the step (1) is preferably undertaken by homogenizer;
The time of the stirring described in the step (1) is preferably 4～8min;
Irradiation in the step (4) preferably carries out irradiation by electron accelerator irradiation;
The temperature that expansion described in the step (5) stretches is preferably 150 ℃;
The multiple that expansion described in the step (5) stretches is preferably 2～3 times;
Described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve can be widely used in the strict fields of environmental requirement such as subway, Highrise buildings, communal facility.
The present invention compared with prior art has following beneficial effect:
(1) only added the inorganic combustion inhibitor of minute quantity in the formula for a product that mould contracting of the present invention is overlapped, the consistency that reaches between resin and phosphorus nitrogen expansion type combustion inhibitor between each component of resin is good, thereby can avoid the decline of mechanical property and the processing characteristics of goods, reduce the waster rate, make high-quality mould contracting cover, preparation method of the present invention is not high to equipment requirements simultaneously, and production cost is moderate.
(2) formulating of recipe among the present invention meets the environment protection requirement that current internationalization is advocated, the mould contracting cover product flame retardant properties of preparation is excellent, the amount of being fuming is little, kept simultaneously good mechanical property, electrical insulation capability, resistance toheat and processing characteristics, mould contracting cover of the present invention can be widely used in the strict fields of environmental requirement such as subway, Highrise buildings, communal facility.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 40kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 40kg, linear low density polyethylene (LLDPE, Saudi Aribian Basic Industry Company, trade mark 218-W, melt index is 2g/10min, and density is 0.918g/cm
3) 5kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 15kg, phosphorus-nitrogen expanding fire retardant A (Asahi Denka Co., Ltd., FP-2200) 43kg, polyethylene wax (Huiyang, Huizhou City forever blue or green chemical industry company limited) 3kg, 0.5kg antioxidant 1010, thio-2 acid two (14) ester 2kg, Viscoat 295 2.5kg and black agglomerate 8kg add homogenizer (model SHR-10A, Zhangjiagang hundred million sharp mechanical company limiteds, stirring velocity is 800RPM, following examples are together) in, high-speed stirring 5 minutes, temperature of charge is controlled in 80 ℃ of scopes; Then with said mixture twin screw extruder (dissection type corotating twin-screw mixing extruder, model PSHJ-35-40L/D, the Jiangyin City, Jiangsu newly reaches molding machine company limited, following examples with) under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use rumbatron (model ELV-8, Novosibirsk,Russia Ahmedabad gram nuclear physics institute, following examples are together) irradiation, irradiation dose is 8Mrad, above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, and cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve for preparing according to the method described above, main performance index following (following examples testing method is all with embodiment 1): flame retardant test reaches FV-0 level (GB 2408-1996); Tensile strength 13.19MPa, elongation at break 529.3% (ASTM D 412); Aging (150 ± 2 ℃, 168h) rear tensile strength 12.79MP, elongation at break 483.5% (ASTM D3045); Dielectric strength 27kV/mm (ASTM D 149); Thermal shocking: 225 ℃, 4 hours, flawless (GJB 150.3A-2009); Low-temperature pliability :-55 ℃, 4 hours, flawless (GJB 150.4A-2009); Volume specific resistance 〉=10
16Ω cm (ASTM D257); Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Embodiment 2
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 40kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 40kg, linear low density polyethylene (LLDPE, Saudi Aribian Basic Industry Company, trade mark 218-W, melt index is 2g/10min, and density is 0.918g/cm
3) 5kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 15kg, phosphorus-nitrogen expanding fire retardant A (Asahi Denka Co., Ltd., FP-2200) 34kg, expansible black lead (median size 400 orders, median size is 150ml/g, sky, Qingdao City and graphite company limited) 10kg, polyethylene wax 3kg, 0.5kg antioxidant 1010, thio-2 acid two (14) ester 2kg, Viscoat 295 2.5kg and black agglomerate 8kg add in the homogenizer, high-speed stirring 5 minutes, temperature of charge are controlled in 80 ℃ of scopes; Then with said mixture with twin screw extruder under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use electron accelerator irradiation, irradiation dose is 8Mrad, and the above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve for preparing according to the method described above, main performance index is as follows: flame retardant test reaches FV-0 level (GB 2408-1996); Tensile strength 12.76MPa, elongation at break 524.1% (ASTM D 412); Aging (150 ± 2 ℃, 168h) rear tensile strength 12.53MP, elongation at break 497.6%; Thermal shocking: 225 ℃, 4 hours, flawless (GJB 150.3A-2009); Low-temperature pliability :-55 ℃, 4 hours, flawless (GJB 150.4A-2009); Volume specific resistance 〉=10
15Ω cm (ASTM D 257); Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Embodiment 3
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 50kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, and melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 40kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, and melt index is 1.1g/10min, and Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 10kg, phosphorus-nitrogen expanding fire retardant B (general match furan (Qingyuan City) phosphorus chemistry company limited, EPFR-100D) 67kg, Zinic stearas (ZnSt) 1kg, 0.25kg antioxidant 1076, Tyox B 0.25kg, triallyl isocyanate 1kg and black agglomerate 5kg add in the homogenizer, high-speed stirring 8 minutes, temperature of charge are controlled in 80 ℃ of scopes; Then with said mixture with twin screw extruder under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use electron accelerator irradiation, irradiation dose is 8Mrad, and the above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The contracting of the low-smoke non-halogen flame-retardant mould of preparation is overlapped according to the method described above, and main performance index is as follows: flame retardant test reaches FV-0 level (GB 2408-1996); Tensile strength 11.79MPa, elongation at break 515.3%; Aging (150 ± 2 ℃, 168h) rear tensile strength 10.81MPa, elongation at break 484.7%; Dielectric voltage withstand: 2500V 60 seconds, does not puncture; Dielectric strength 14.69kV/mm; Thermal shocking: 225 ℃, 4 hours, flawless; Low-temperature pliability :-55 ℃, 4 hours, flawless; Volume specific resistance 〉=10
14Ω cm; Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Embodiment 4
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 50kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 40kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 10kg, phosphorus-nitrogen expanding fire retardant B (EPFR-100D that general match furan (Qingyuan City) phosphorus chemistry company limited produces) 50kg, expansible black lead (median size 400 orders, median size is 150ml/g, sky, Qingdao City and graphite company limited) 10kg, Zinic stearas (ZnSt) 1kg, 0.25kg antioxidant 1076, Tyox B 0.25kg, triallyl isocyanate 1kg and black agglomerate 5kg add in the homogenizer, high-speed stirring 8 minutes, temperature of charge are controlled in 80 ℃ of scopes; Then with said mixture with twin screw extruder under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use electron accelerator irradiation, irradiation dose is 8Mrad, and the above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The contracting of the low-smoke non-halogen flame-retardant mould of preparation is overlapped according to the method described above, and main performance index is as follows: flame retardant test reaches FV-0 level (GB 2408-1996); Tensile strength 11.62MPa, elongation at break 513.5%; Aging (150 ± 2 ℃, 168h) rear tensile strength 10.68MPa, elongation at break 510.7%; Thermal shocking: 225 ℃, 4 hours, flawless; Low-temperature pliability :-55 ℃, 4 hours, flawless; Volume specific resistance 〉=10
14Ω cm; Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Embodiment 5
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 45kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, and melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 35kg, terpolymer EP rubber (Jilin Petrochemical EPDM J-4045) 5kg, linear low density polyethylene (LLDPE, Saudi Aribian Basic Industry Company, trade mark 218-W, melt index are 2g/10min, and density is 0.918g/cm
3) 10kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 5kg, phosphorus-nitrogen expanding fire retardant A (Asahi Denka Co., Ltd., FP-2200) 10kg, phosphorus-nitrogen expanding fire retardant B (EPFR-100D that general match furan (Qingyuan City) phosphorus chemistry company limited produces) 40kg, (median size is 400 orders to expansible black lead, expansion multiplying power is 150ml/g, carbon content is 90-99.9%) 12kg, Magnesium Stearate 2kg, the 1kg antioxidant 1010, tetramethylol methane tetraacrylate 2kg and black agglomerate 6kg, add in the homogenizer, high-speed stirring 6 minutes, temperature of charge are controlled in 80 ℃ of scopes; Then with said mixture with twin screw extruder under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use electron accelerator irradiation, irradiation dose is 10Mrad, and the above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The contracting of the low-smoke non-halogen flame-retardant mould of preparation is overlapped according to the method described above, and main performance index is as follows: flame retardant test reaches the FV-1 level; Tensile strength 14.38MPa, elongation at break 496.8%; Aging (150 ± 2 ℃, 168h) rear tensile strength 14.17MPa, elongation at break 476.9%; Dielectric voltage withstand: 2500V 60 seconds, does not puncture; Dielectric strength 15.74kV/mm; Thermal shocking: 225 ℃, 4 hours, flawless; Low-temperature pliability :-55 ℃, 4 hours, flawless; Volume specific resistance 〉=10
16Ω cm; Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Embodiment 6
Get ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 28% quality, melt index is 4.5g/10min, France atropic Fenner Inc., the trade mark is EVAtane 2803) 45kg, ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, and melt index is 3.5g/10min, Mitsui group, the trade mark is P1405) 35kg, terpolymer EP rubber 5kg, linear low density polyethylene (LLDPE, Saudi Aribian Basic Industry Company, trade mark 218-W, melt index are 2g/10min, and density is 0.918g/cm
3) 10kg, (percentage of grafting is 1.2% to maleic anhydride functional group grafted ethene-vinyl acetate copolymer, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, the trade mark is JCP-851) 5kg, phosphorus-nitrogen expanding fire retardant A (Asahi Denka Co., Ltd., FP-2200) 26kg, phosphorus-nitrogen expanding fire retardant B (EPFR-100D that general match furan (Qingyuan City) phosphorus chemistry company limited produces) 12kg, (median size is 400 orders to expansible black lead, expansion multiplying power is 150ml/g, carbon content is 90-99.9%) 16kg, Magnesium Stearate 2kg, the 1kg antioxidant 1010, tetramethylol methane tetraacrylate 2kg and black agglomerate 6kg, add in the homogenizer, high-speed stirring 6 minutes, temperature of charge are controlled in 80 ℃ of scopes; Then with said mixture with twin screw extruder under 100-160 ℃ of temperature, extrude, wire drawing, air-cooled, pelletizing.Again the pressure injection in special mould of the pellet after the above-mentioned pelletizing is become mould contracting cover, then use electron accelerator irradiation, irradiation dose is 12Mrad, and the above-mentioned mould contracting behind the cross-linking radiation is enclosed within 150 ℃ of lower artificial expansions and stretches after 3 times, cooling and shaping obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve again.
The contracting of the low-smoke non-halogen flame-retardant mould of preparation is overlapped according to the method described above, and main performance index is as follows: flame retardant test reaches the FV-0 level; Tensile strength 14.31MPa, elongation at break 476.6%; Aging (150 ± 2 ℃, 168h) rear tensile strength 13.87MPa, elongation at break 451.9%; Thermal shocking: 225 ℃, 4 hours, flawless; Low-temperature pliability :-55 ℃, 4 hours, flawless; Volume specific resistance 〉=10
16Ω cm; Salt spray resistance reaches the requirement of Military Standards GJB150.11-86; Copper corrosion: 135 ± 2 ℃, 16 hours, without corrosion; Meet the requirement of the environmental protection standards such as EN1122, EPA3050B, EPA3052, EN14582 and the RoHS of European Union environmental protection instruction.
Comparative Examples 1
Adopt the preparation method identical with embodiment 2, replace phosphorus-nitrogen expanding fire retardant A 34kg, expansible black lead 10kg, other components unchanged of filling a prescription with massfractions such as traditional expanding fire retardant ammonium polyphosphate 26kg, melamine cyanurate 9kg, tetramethylolmethane 9kg.The mould of preparation contracting cover flame retardant properties is poor according to the method described above, and difficulty is put out certainly, and produces molten in the combustion processes.Comparing result shows, the collaborative expansible black lead fire retardant polyolefin effect of phosphorus-nitrogen expanding fire retardant A is excellent, the carbon residue amount is larger in the combustion processes, and the charcoal layer is fine and close, effectively play the effect of heat insulation matter, and the vermiform carbon structure that the high expansion of expansible black lead produces plays effective supporting role to combustionmaterial, has suppressed molten generation.
Comparative Examples 2
Adopt the preparation method identical with embodiment 4, use ammonium polyphosphate flame retardant 40kg, (median size is 400 orders to expansible black lead, expansion multiplying power is 150ml/g, carbon content is 90-99.9%) massfraction such as 20kg replaces phosphorus-nitrogen expanding fire retardant B 50kg, expansible black lead 10kg, other components unchanged of filling a prescription.The contracting of the mould of preparation is overlapped according to the method described above, and flame retardant test reaches the FV-1 level; Tensile strength 12.74MPa, elongation at break 512.5%; After room temperature was placed 72h, it was serious to go out frost, poor stability.Comparing result shows, under the identical prerequisite of addition, phosphorus-nitrogen expanding fire retardant B is than ammonium polyphosphate synergetic expansible black lead fire retardant polyolefin better effects if, only has the fire-retardant rank that when ammonium polyphosphate and expansible black lead consumption are very large, just can reach FV-0, but it is serious that frost is extracted in the standby mould contracting of this legal system, so need to will use after the modifications such as ammonium polyphosphate do coating, thereby improve cost, and a large amount of interpolations of fire retardant can reduce mechanical property, the processing characteristics of goods.
Comparative Examples 3
Adopt the preparation method identical with embodiment 3, with ethylene-vinyl acetate copolymer (EVA, the content of vinyl-acetic ester accounts for 14% quality, melt index is 3.5g/10min, and Mitsui group, the trade mark is P1405) etc. massfraction replace maleic anhydride functional group grafted ethene-vinyl acetate copolymer (percentage of grafting be 1.2%, melt index is 1.1g/10min, Shanghai is poly-macromolecular material company limited for a long time, and the trade mark is JCP-851), other components unchanged of filling a prescription.Mechanical properties decrease, tensile strength 10.63MPa, elongation at break 416.7% are overlapped in the contracting of the mould of preparation according to the method described above.Comparing result shows, the polar functional group absorption powder ability of maleic anhydride functional group grafted ethene-vinyl acetate copolymer (JCP-851) is strong, powder is disperseed in resin system better, avoid the generation of focal point of stress, promote the consistency of composite system, show the rising of mould contracting cover product tensile strength and elongation at break.Good consistency has improved the flowability of blend composition when extrusion processing simultaneously, thereby enhances productivity.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve is characterized in that comprising following composition by mass parts:
85～95 parts of polyolefin resines
5～15 parts of the ethylene-vinyl acetate copolymers of maleic anhydride modification by copolymerization
30～70 parts of nitrogen phosphorus series expansion type halogen-free flame retardantss
0～16 part of expansible black lead
1～3 part of lubricant
0.5～2.5 part of antioxidant
1～2.5 part of sensitizing agent
5～8 parts of black agglomerates;
Described polyolefin resin is at least a in ethylene-vinyl acetate copolymer, linear low density polyethylene or the terpolymer EP rubber;
Described ethylene-vinyl acetate copolymer is that the mass content of vinyl-acetic ester is 14～28%, melt index is the ethylene-vinyl acetate copolymer of 3.5～4.5g/10min;
Described linear low density polyethylene is that melt index is 2g/10min, and density is 0.918g/cm
3Linear low density polyethylene;
Described terpolymer EP rubber is that the ethene mass content is 50～65%, and mooney viscosity ML125 ℃ 1+4 is the terpolymer EP rubber of 38～52MU;
Described nitrogen phosphorus series expansion type halogen-free flame retardants is one or both among phosphorus nitrogen expansion type combustion inhibitor A or the phosphorus nitrogen expansion type combustion inhibitor B;
Described phosphorus nitrogen expansion type combustion inhibitor A is that phosphorus content is 16～20%, and nitrogen content is that 19～23%, 50%D is 5.0 μ m, and 90%D is 11.0 μ m, and decomposition temperature is greater than 270 ℃ phosphorus nitrogen expansion type combustion inhibitor;
Described phosphorus nitrogen expansion type combustion inhibitor B is that phosphorus content is 22～24%, and nitrogen content is 20～22%, the about 10 μ m of median size, and decomposition temperature is greater than 260 ℃ phosphorus nitrogen expansion type combustion inhibitor.
2. low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve according to claim 1 is characterized in that:
Described phosphorus nitrogen expansion type combustion inhibitor A is the FP-2200 nitrogen phosphorus series expansion type halogen-free flame retardants that Asahi Denka Co., Ltd. produces;
Described phosphorus nitrogen expansion type combustion inhibitor B is the EPFR-100D phosphorous-nitrogen system bittern-free fire retardant that general match furan (Qingyuan City) phosphorus chemistry company limited produces.
3. low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve according to claim 1 is characterized in that:
The ethylene-vinyl acetate copolymer of described maleic anhydride modification by copolymerization is that percentage of grafting is quality percentage composition 1.0～1.2%, and melt index is the ethylene-vinyl acetate copolymer of the maleic anhydride modification by copolymerization of 1.1～2.0g/10min;
Described expansible black lead is that median size is that 200～400 orders, expansion multiplying power are that 150～200ml/g, carbon content are the expansible black lead of mass percent 90～99.9%;
Described lubricant is at least a in Zinic stearas, Magnesium Stearate or the polyethylene wax;
Described antioxidant be hindered phenol primary antioxidant and the efficient auxiliary antioxidant of thioether in mass ratio 1:1～4 proportionings get;
Described sensitizing agent is at least a in Viscoat 295, tetramethylol methane tetraacrylate or the triallyl isocyanate;
Described black agglomerate is BLACK II black agglomerate.
4. low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve according to claim 3 is characterized in that:
Described hindered phenol primary antioxidant is one or both in four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters or β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid;
The efficient auxiliary antioxidant of described thioether is one or both in Tyox B or thio-2 acid two (18) ester.
5. the preparation method of each described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve of claim 1～4 is characterized in that comprising the steps:
(1) ethylene-vinyl acetate copolymer, 30～70 mass parts nitrogen phosphorus series expansion type halogen-free flame retardantss, 0～16 mass parts expansible black lead, 1～3 mass parts lubricant, 0.5～2.5 mass parts antioxidant, 1～2.5 mass parts sensitizing agent and 5～8 mass parts black agglomerates with 85～95 mass parts polyolefin resines, 5～15 mass parts maleic anhydride modifications by copolymerization pass through stirring and evenly mixing, temperature of charge is controlled within 80 ℃ in the whipping process, obtains mixture;
(2) with mixture with twin screw extruder in 100～160 ℃ extrude, wire drawing, air-cooled, pelletizing;
(3) the pellet pressure injection after the above-mentioned pelletizing is become mould contracting cover;
(4) the mould contracting cover that step (3) is obtained carries out irradiation, and irradiation dose is 8～12Mrad;
(5) again the contracting of the mould behind the cross-linking radiation is placed in 140～160 ℃ of expansion stretchings, cooling and shaping, obtains low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve.
6. the preparation method of low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve according to claim 5 is characterized in that:
Temperature of charge described in the step (1) is for being controlled at 70～80 ℃;
Irradiation described in the step (4) is for to carry out irradiation by rumbatron;
The multiple that expansion described in the step (5) stretches is 2～3 times.
7. the application of low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve according to claim 6 is characterized in that: described low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve is applied to the strict field of environmental requirement in the communal facility;
Described environmental requirement strictly refers to the requirement that meets EN1122, EPA3050B, EPA3052, EN14582 environmental protection standard and the RoHS of European Union environmental protection instruction.
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| CN103450668B (en) * | 2013-08-07 | 2016-08-10 | 上海日之升新技术发展有限公司 | High-strength carbon fiber strengthens halogen-free flameproof PA6 composite and preparation method thereof |
| CN106928531A (en) * | 2015-12-29 | 2017-07-07 | 天津市普立泰高分子科技有限公司 | Expansion type halogen-free high fire-retardance polyethylene sheath material and preparation method thereof |
| CN105694518A (en) * | 2016-03-18 | 2016-06-22 | 建湖东方电缆材料有限公司 | Hot material type halogen-free low-smoke flame-retardant sheath material |
| CN110804134A (en) * | 2019-11-18 | 2020-02-18 | 江苏东方电缆材料有限公司 | Halogen-free flame-retardant silane self-crosslinking cable material and preparation method thereof |
| CN114228101A (en) * | 2021-11-11 | 2022-03-25 | 中广核拓普（四川）新材料有限公司 | High-speed extrusion casting-free halogen-free low-smoke flame-retardant polyolefin cable material and preparation method thereof |
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