CN105400057A - Halogen-free flame-retardant temperature-resistant polyolefin pyrocondensation material and preparation method thereof - Google Patents
Halogen-free flame-retardant temperature-resistant polyolefin pyrocondensation material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/08—Copolymers of ethene
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Abstract
The invention discloses a halogen-free flame-retardant temperature-resistant polyolefin pyrocondensation material and a preparation scheme thereof. The material is prepared from, by weight, 20-100 parts of linear low-density polyethylene, 10-80 parts of vinyl copolymer, 0.5-5 parts of sensitizer, 5-20 parts of silicone flame retardant, 5-50 parts of inorganic flame retardant, 5-40 parts of phosphorus-nitrogen containing flame retardant, 1-5 parts of antioxidant, 1-5 parts of light stabilizer and 1-20 parts of smoke restraining agent. The halogen-free flame-retardant temperature-resistant polyolefin pyrocondensation material obtained through the preparation method can reach the high temperature resistant level of 150 DEG C or higher, is good in combustion resistant effect, can not release harmful gas, is not prone to spontaneous combustion, reduces potential safety hazards, is low in cost and high in cost performance, and can be widely applied to the fields of locomotives, aviation, electrons, ships, nuclear power, the war industry and the like.
Description
Technical field
The present invention relates to a kind of halogen-free flameproof heatproof polyolefine material contracting with heat and preparation method thereof.
Background technology
Heat-shrinkable T bush is widely used in the fields such as electronics, locomotive, aviation, boats and ships, nuclear power, military project; Heat-shrinkable T bush kind is in the market a lot, has different classification according to characteristic functions and different materials; Along with improving constantly of people's awareness of safety, environmental protection flame retardant heat-shrink tube is the main product of existing market; But great majority 150 DEG C of grade high temperature heat-resistant Heat-Shrinkable Tubings generally use halogen containing flame-retardant to meet flame-retardancy requirements or use containing red phosphorus combustion inhibitor now; Halogen flame-retardant system discharges the carcinogenic toxic gas of dioxin one-level in combustion, discharges irritating smog containing in red phosphorus flame-retardant system combustion processes, and meeting spontaneous combustion after being subject to friction, impact in production process, there is serious potential safety hazard.
Halogen heat-shrink tube in the market or electric wire temperature resistant grade are mainly between 90-135 DEG C, be difficult to reach 150 DEG C of grades, generally use the polymer base material of high price as fluoroplastics if reach 150 DEG C or more grades, but fluoroplastics are expensive, and fluorine can be separated out by trace in fluoro-containing plastic heat-shrink tube production process, the operation of employee's long campaigns contact fluorine heat-shrink tube can cause certain influence to health.
The field develop rapidlys such as current China locomotive, aviation, boats and ships, nuclear power and military project, very urgent to the demand of high-performance high performance-price ratio product, therefore we have developed and aly can meet the material contracting with heat that environmental protection flame retardant requirement has resistance to 150 DEG C of grades simultaneously, this material can be applied and heat-shrink tube product, electric wire product and other suitable products.
Summary of the invention
For the technical problem of above-mentioned existence, the object of the invention is: propose a kind of halogen-free flameproof heatproof polyolefine material contracting with heat and preparation method thereof.
Technical solution of the present invention is achieved in that a kind of halogen-free flameproof heatproof polyolefine material contracting with heat, comprises the component of following parts by weight:
The linear low density polyethylene of 20-100 weight part;
The ethylenic copolymer of 10-80 weight part;
The sensitizing agent of 0.5-5 weight part;
The silicone flame retardant of 5-20 weight part;
The inorganic combustion inhibitor of 5-50 weight part;
The phosphorus-nitrogen containing flame retardant of 5-40 weight part;
The oxidation inhibitor of 1-5 weight part;
The photostabilizer of 1-5 weight part;
The smoke suppressant of 1-20 weight part.
Preferably, described linear low density polyethylene, its melting index 1-10g/10min, tensile strength is greater than 15MPa, and elongation at break is greater than 400%.
Preferably, described ethylenic copolymer comprises: terpolymer EP rubber, plastic of poly vinyl acetate, ethylene methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, POE; Wherein, the mooney viscosity of described ethylene-propylene diene copolymer index is 10-60, and ethylene content is between 40-80%; In described plastic of poly vinyl acetate, vinyl acetate content is between 5-28%, and melting index is between 1.0-5.5g/10min; In described ethylene methyl acrylate copolymer, acrylate content is between 8-25%, and melting index is between 0.5-4.0g/10min; In described POE, octene content is between 5-25%, and melting index is between 0.5-3.5g/10min.
Preferably, described sensitizing agent comprises: at least one in the middle of trimethylolpropane trimethacrylate, Viscoat 295, triallyl isonitrile urea acid esters, triallyl nitrile urea acid esters, dimethacrylate Tetraglycol 99 ester, diacrylate Tetraglycol 99 ester, tri (propylene glycol) diacrylate, propylene glycol diacrylate.
Preferably, described silicone flame retardant comprises silicone resin based flame retardant and/or poly-silicon boranes fire retardant; Described inorganic combustion inhibitor comprises: at least one in the middle of aluminium hydroxide, zinc borate, magnesium hydroxide.
Preferably, described phosphorus-nitrogen containing flame retardant comprises: at least one in the middle of trimeric cyanamide, tetramethylolmethane, polyphosphate, six phenyl ring tripolyphosphazenes, melamine cyanurate, melamine polyphosphate, urea, Dyhard RU 100.
Preferably, described oxidation inhibitor antioxidant packages contains: at least one in the middle of Hinered phenols antioxidant, aromatic amine oxidation inhibitor, auxiliary antioxidant; Wherein, Hinered phenols antioxidant comprises 2,6-, tri-grades of butyl-4-methylphenols, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester; Aromatic amine oxidation inhibitor comprises pentanoic, Ursol D and dihydroquinoline; Auxiliary antioxidant comprise two Lauryl Alcohol ester, two ten four carbon alcohols esters and two octadecanol ester, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester.
Preferably, described photostabilizer comprises: at least one in the middle of Octabenzone, three (1,2,2,6,6-pentamethvl base) phosphorous acid ester, poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester.
Preferably, described smoke suppressant comprises: at least one in the middle of zinc borate, molybdic oxide, ammonium octamolybdate, ten ammonium molybdates, zinc molybdate base complex, ferrocene.
Prepare the method for above-mentioned halogen-free flameproof heatproof polyolefine material contracting with heat, comprise following steps:
(1) linear low density polyethylene, ethylenic copolymer, sensitizing agent, silicone flame retardant, inorganic combustion inhibitor, phosphorus-nitrogen containing flame retardant, oxidation inhibitor, photostabilizer, smoke suppressant are pressed said components at the temperature of 50-80 DEG C, plasticate evenly in Banbury mixer;
(2) will plasticate uniform mixture by twin screw further mixing even while granulation, obtain the polyolefine pyrocondensation masterbatch with halogen-free flameproof temperature-resistance characteristic;
(3) this masterbatch is passed through extrusion moulding;
(4) by the material that obtains with this master batch extrusion moulding radiation modification by rumbatron, the high molecular polymer in material is occurred crosslinked;
(5) material crossed by cross-linking radiation is expanded under the high temperature of 130-160 DEG C, makes this material under expansion state in room temperature or lower than cooling and shaping under room temperature condition simultaneously.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages:
Utilize said components, and by halogen-free flameproof heatproof polyolefine material contracting with heat that above-mentioned preparation method obtains, the high temperature resistant grade of more than 150 DEG C can be reached, good flame retardation effect, can not discharge obnoxious flavour, not easily spontaneous combustion, reduce potential safety hazard, cost is lower, and cost performance is high, can be widely used in the fields such as locomotive, aviation, electronics, boats and ships, nuclear power, military project.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1: a kind of halogen-free flameproof heatproof polyolefine material contracting with heat, comprises following component:
The linear low density polyethylene of 20 weight parts;
The ethylenic copolymer of 10 weight parts;
The sensitizing agent of 0.5 weight part;
The silicone flame retardant of 5 weight parts;
The inorganic combustion inhibitor of 5 weight parts;
The phosphorus-nitrogen containing flame retardant of 5 weight parts;
The oxidation inhibitor of 1 weight part;
The photostabilizer of 1 weight part;
The smoke suppressant of 1 weight part.
Embodiment 2: a kind of halogen-free flameproof heatproof polyolefine material contracting with heat, comprises following component:
The linear low density polyethylene of 60 weight parts;
The ethylenic copolymer of 45 weight parts;
The sensitizing agent of 3 weight parts;
The silicone flame retardant of 12.5 weight parts;
The inorganic combustion inhibitor of 25 weight parts;
The phosphorus-nitrogen containing flame retardant of 20 weight parts;
The oxidation inhibitor of 3 weight parts;
The photostabilizer of 3 weight parts;
The smoke suppressant of 10 weight parts.
Embodiment 3: a kind of halogen-free flameproof heatproof polyolefine material contracting with heat, comprises following component:
The linear low density polyethylene of 100 weight parts;
The ethylenic copolymer of 80 weight parts;
The sensitizing agent of 5 weight parts;
The silicone flame retardant of 20 weight parts;
The inorganic combustion inhibitor of 50 weight parts;
The phosphorus-nitrogen containing flame retardant of 40 weight parts;
The oxidation inhibitor of 5 weight parts;
The photostabilizer of 5 weight parts;
The smoke suppressant of 20 weight parts.
Embodiment 4-10: with reference to implementing 1-3, change the parts by weight of each component, as shown in the table:
| Composition component | Linear low density polyethylene | Ethylenic copolymer | Sensitizing agent | Silicone flame retardant | Inorganic combustion inhibitor | Phosphorus-nitrogen containing flame retardant | Oxidation inhibitor | Photostabilizer | Smoke suppressant |
| Embodiment 4 | 25 | 15 | 0.5 | 5 | 5 | 5 | 1 | 1 | 1 |
| Embodiment 5 | 30 | 20 | 1 | 8 | 10 | 10 | 1.5 | 1.5 | 4 |
| Embodiment 6 | 40 | 30 | 2 | 10 | 20 | 15 | 2 | 2 | 7 |
| Embodiment 7 | 50 | 40 | 2.5 | 12 | 25 | 20 | 2.5 | 2.5 | 10 |
| Embodiment 8 | 60 | 50 | 3 | 15 | 30 | 25 | 3 | 3 | 13 |
| Embodiment 9 | 70 | 60 | 4 | 18 | 40 | 30 | 4 | 4 | 16 |
| Embodiment 10 | 90 | 70 | 5 | 20 | 50 | 40 | 5 | 5 | 20 |
Wherein, described linear low density polyethylene, melting index 1-10g/10min, tensile strength is greater than 15MPa, and elongation at break is greater than 400%.
Described ethylenic copolymer comprises terpolymer EP rubber, plastic of poly vinyl acetate, ethylene methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, POE; The mooney viscosity (ML1+4100) of described ethylene-propylene diene copolymer index is at 10-60, and ethylene content is between 40-80%; In described plastic of poly vinyl acetate, vinyl acetate content is between 5-28%, and melting index MI is between 1.0-5.5g/10min; In described ethylene methyl acrylate copolymer, acrylate content is between 8-25%, and melting index MI is between 0.5-4.0g/10min; In described POE, octene content is between 5-25%, and melting index MI is between 0.5-3.5g/10min.
Described sensitizing agent is a kind of, the two kinds or more of mixture in following material, comprising: trimethylolpropane trimethacrylate (TMPTMA), Viscoat 295 (TMPTA), triallyl isonitrile urea acid esters (TAIC), triallyl nitrile urea acid esters (TAC), dimethacrylate Tetraglycol 99 ester (TEGDM), diacrylate Tetraglycol 99 ester (TEGDA), tri (propylene glycol) diacrylate (TPGDA), propylene glycol diacrylate (DPGDA).
One or both mixture in the following material of described silicone flame retardant, comprising: silicone resin based flame retardant, poly-silicon boranes fire retardant.
Described inorganic combustion inhibitor is the mixture of one or more in aluminium hydroxide, zinc borate, magnesium hydroxide.
Described phosphorus-nitrogen containing flame retardant is a kind of, the two kinds or more of mixture in following material, comprising: trimeric cyanamide, tetramethylolmethane, polyphosphate, six phenyl ring tripolyphosphazenes, melamine cyanurate, melamine polyphosphate, urea, Dyhard RU 100 etc.
Described oxidation inhibitor is a kind of, the two kinds or more of mixture in the middle of Hinered phenols antioxidant, aromatic amine oxidation inhibitor and auxiliary antioxidant; Wherein, Hinered phenols antioxidant comprises: 2,6-, tri-grades of butyl-4-methylphenols, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester etc.; Aromatic amine oxidation inhibitor comprises: the compounds such as pentanoic, Ursol D and dihydroquinoline and derivative thereof or polymkeric substance; Auxiliary antioxidant comprises: two Lauryl Alcohol ester, two ten four carbon alcohols esters and two octadecanol ester, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester etc.
Described photostabilizer is a kind of, the two kinds or more of mixture in following material, comprising: Octabenzone; Three (1,2,2,6,6-pentamethvl base) phosphorous acid ester; Poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester.
Described smoke suppressant is a kind of, the two kinds or more of mixture in following material: zinc borate, molybdic oxide, ammonium octamolybdate, ten ammonium molybdates, zinc molybdate base complex, ferrocene etc.
Can be found out by the data of above each embodiment, halogen-free flameproof heatproof polyolefine material contracting with heat of the present invention, have higher high temperature resistant grade and flame retardant effect, and can not discharge obnoxious flavour, not easily spontaneous combustion, reduces potential safety hazard; The fields such as locomotive, aviation, electronics, boats and ships, nuclear power, military project can be widely used in.
The material step preparation by the following method of the various embodiments described above, comprising:
Embodiment 1:(1) in the following order linear low density polyethylene, ethylenic copolymer, oxidation inhibitor, photostabilizer, inorganic combustion inhibitor, silicone flame retardant, phosphorus-nitrogen containing flame retardant, smoke suppressant, sensitizing agent are pressed above-mentioned parts by weight at the temperature of 50 DEG C, plasticate evenly in Banbury mixer;
(2) will plasticate uniform mixture by twin screw further mixing even while granulation, obtain the polyolefine pyrocondensation masterbatch with halogen-free flameproof temperature-resistance characteristic;
(3) this masterbatch is obtained heat-shrinkable T bush by extrusion moulding;
(4) by the heat-shrinkable T bush that obtains with this master batch extrusion moulding radiation modification by rumbatron, the high molecular polymer in material is occurred crosslinked;
(5) heat-shrinkable T bush crossed by cross-linking radiation is expanded at the temperature of 130 DEG C, makes this material in room temperature or lower than cooling and shaping under room temperature condition under expansion state simultaneously, obtains the heat-shrinkable T bush with halogen-free flameproof temperature-resistance characteristic.
The performance of the heat-shrinkable T bush obtained is as follows:
Tensile strength: 14.5MPa;
Elongation at break: 395%;
Flame retardant resistance: pass through VW-1;
Aging rear intensity (180 ± 1 DEG C, 168h): 13MPa;
Aging rear elongation at break (180 ± 1 DEG C, 168h): 351%.
Embodiment 2:(1) in the following order linear low density polyethylene, ethylenic copolymer, oxidation inhibitor, photostabilizer, inorganic combustion inhibitor, silicone flame retardant, phosphorus-nitrogen containing flame retardant, smoke suppressant, sensitizing agent are pressed above-mentioned parts by weight at the temperature of 65 DEG C, plasticate evenly in Banbury mixer;
(2) will plasticate uniform mixture by twin screw further mixing even while granulation, obtain the polyolefine pyrocondensation masterbatch with halogen-free flameproof temperature-resistance characteristic;
(3) this masterbatch is obtained heat-shrinkable T bush by extrusion moulding;
(4) by the heat-shrinkable T bush that obtains with this master batch extrusion moulding radiation modification by rumbatron, the high molecular polymer in material is occurred crosslinked;
(5) heat-shrinkable T bush crossed by cross-linking radiation is expanded at the temperature of 145 DEG C, makes this material in room temperature or lower than cooling and shaping under room temperature condition under expansion state simultaneously, obtains the heat-shrinkable T bush with halogen-free flameproof temperature-resistance characteristic.
The performance of the heat-shrinkable T bush obtained is as follows:
Tensile strength: 15.2MPa;
Elongation at break: 416%;
Flame retardant resistance: pass through VW-1;
Aging rear intensity (180 ± 1 DEG C, 168h): 12.9MPa;
Aging rear elongation at break (180 ± 1 DEG C, 168h): 365%.
Embodiment 3:(1) in the following order linear low density polyethylene, ethylenic copolymer, oxidation inhibitor, photostabilizer, inorganic combustion inhibitor, silicone flame retardant, phosphorus-nitrogen containing flame retardant, smoke suppressant, sensitizing agent are pressed above-mentioned parts by weight at the temperature of 80 DEG C, plasticate evenly in Banbury mixer;
(2) will plasticate uniform mixture by twin screw further mixing even while granulation, obtain the polyolefine pyrocondensation masterbatch with halogen-free flameproof temperature-resistance characteristic;
(3) this masterbatch is obtained heat-shrinkable T bush by extrusion moulding;
(4) by the heat-shrinkable T bush that obtains with this master batch extrusion moulding radiation modification by rumbatron, the high molecular polymer in material is occurred crosslinked;
(5) heat-shrinkable T bush crossed by cross-linking radiation is expanded at the temperature of 160 DEG C, makes this material in room temperature or lower than cooling and shaping under room temperature condition under expansion state simultaneously, obtains the heat-shrinkable T bush with halogen-free flameproof temperature-resistance characteristic.
The performance of the heat-shrinkable T bush obtained is as follows:
Tensile strength: 13.6MPa;
Elongation at break: 361%;
Flame retardant resistance: pass through VW-1;
Aging rear intensity (180 ± 1 DEG C, 168h): 11.3MPa;
Aging rear elongation at break (180 ± 1 DEG C, 168h): 295%.
Embodiment 4-10: with reference to implementing 1-3, change the parts by weight of each component, as shown in the table:
| Plasticating temperature | Expansion temperature | Tensile strength | Elongation at break | Flame retardant resistance | Aging rear intensity | Aging rear elongation at break | |
| Embodiment 4 | 50 | 160 | 15.9 | 470% | Do not pass through VW-1 | 14.5 | 396% |
| Embodiment 5 | 55 | 155 | 14.2 | 387% | Pass through VW-1 | 12.3 | 325% |
| Embodiment 6 | 60 | 150 | 13.4 | 362% | Pass through VW-1 | 11.8 | 286% |
| Embodiment 7 | 65 | 150 | 13.5 | 370% | Pass through VW-1 | 11.5 | 301% |
| Embodiment 8 | 70 | 140 | 12.9 | 395% | Pass through VW-1 | 10.7 | 290% |
| Embodiment 9 | 75 | 135 | 11.6 | 351% | Pass through VW-1 | 9.6 | 275% |
| Embodiment 10 | 80 | 130 | 11.4 | 346% | Pass through VW-1 | 9.8 | 281% |
Can be found out by the data of above each embodiment, utilize component of the present invention, and by the halogen-free flameproof heatproof polyolefin thermal shrinkable sleeve pipe that above-mentioned preparation method obtains, there is higher high temperature resistant grade, tensile strength and elongation at break; Its good flame retardation effect, and can not obnoxious flavour be discharged, not easily spontaneous combustion, reduces potential safety hazard; Aging rear intensity and aging rear elongation at break meet service requirements, and its cost is lower, and cost performance is high, can be widely used in the fields such as locomotive, aviation, electronics, boats and ships, nuclear power, military project.
Above-described embodiment is only for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and be implemented; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a halogen-free flameproof heatproof polyolefine material contracting with heat, is characterized in that: the component comprising following parts by weight:
The linear low density polyethylene of 20-100 weight part;
The ethylenic copolymer of 10-80 weight part;
The sensitizing agent of 0.5-5 weight part;
The silicone flame retardant of 5-20 weight part;
The inorganic combustion inhibitor of 5-50 weight part;
The phosphorus-nitrogen containing flame retardant of 5-40 weight part;
The oxidation inhibitor of 1-5 weight part;
The photostabilizer of 1-5 weight part;
The smoke suppressant of 1-20 weight part.
2. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, it is characterized in that: described linear low density polyethylene, its melting index 1-10g/10min, tensile strength is greater than 15MPa, and elongation at break is greater than 400%.
3. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described ethylenic copolymer comprises: terpolymer EP rubber, plastic of poly vinyl acetate, ethylene methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, POE; Wherein, the mooney viscosity of described ethylene-propylene diene copolymer index is 10-60, and ethylene content is between 40-80%; In described plastic of poly vinyl acetate, vinyl acetate content is between 5-28%, and melting index is between 1.0-5.5g/10min; In described ethylene methyl acrylate copolymer, acrylate content is between 8-25%, and melting index is between 0.5-4.0g/10min; In described POE, octene content is between 5-25%, and melting index is between 0.5-3.5g/10min.
4. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described sensitizing agent comprises: at least one in the middle of trimethylolpropane trimethacrylate, Viscoat 295, triallyl isonitrile urea acid esters, triallyl nitrile urea acid esters, dimethacrylate Tetraglycol 99 ester, diacrylate Tetraglycol 99 ester, tri (propylene glycol) diacrylate, propylene glycol diacrylate.
5. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described silicone flame retardant comprises silicone resin based flame retardant and/or poly-silicon boranes fire retardant; Described inorganic combustion inhibitor comprises: at least one in the middle of aluminium hydroxide, zinc borate, magnesium hydroxide.
6. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described phosphorus-nitrogen containing flame retardant comprises: at least one in the middle of trimeric cyanamide, tetramethylolmethane, polyphosphate, six phenyl ring tripolyphosphazenes, melamine cyanurate, melamine polyphosphate, urea, Dyhard RU 100.
7. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described oxidation inhibitor antioxidant packages contains: at least one in the middle of Hinered phenols antioxidant, aromatic amine oxidation inhibitor, auxiliary antioxidant; Wherein, Hinered phenols antioxidant comprises 2,6-, tri-grades of butyl-4-methylphenols, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester; Aromatic amine oxidation inhibitor comprises pentanoic, Ursol D and dihydroquinoline; Auxiliary antioxidant comprise two Lauryl Alcohol ester, two ten four carbon alcohols esters and two octadecanol ester, three monooctyl esters, three the last of the ten Heavenly stems ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester.
8. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, it is characterized in that: described photostabilizer comprises: Octabenzone, three (1,2,2,6,6-pentamethvl base) phosphorous acid ester, poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) at least one in the middle of ester.
9. halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, is characterized in that: described smoke suppressant comprises: at least one in the middle of zinc borate, molybdic oxide, ammonium octamolybdate, ten ammonium molybdates, zinc molybdate base complex, ferrocene.
10. prepare the method for halogen-free flameproof heatproof polyolefine material contracting with heat according to claim 1, it is characterized in that, comprise following steps:
(1) linear low density polyethylene, ethylenic copolymer, sensitizing agent, silicone flame retardant, inorganic combustion inhibitor, phosphorus-nitrogen containing flame retardant, oxidation inhibitor, photostabilizer, smoke suppressant are pressed said components at the temperature of 50-80 DEG C, plasticate evenly in Banbury mixer;
(2) will plasticate uniform mixture by twin screw further mixing even while granulation, obtain the polyolefine pyrocondensation masterbatch with halogen-free flameproof temperature-resistance characteristic;
(3) this masterbatch is passed through extrusion moulding;
(4) by the material that obtains with this master batch extrusion moulding radiation modification by rumbatron, the high molecular polymer in material is occurred crosslinked;
(5) material crossed by cross-linking radiation is expanded under the high temperature of 130-160 DEG C, makes this material under expansion state in room temperature or lower than cooling and shaping under room temperature condition simultaneously.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496755A (en) * | 2016-10-13 | 2017-03-15 | 苏州沃尔兴电子科技有限公司 | A kind of high convergency multiplying power fire retardant thermal shrinkage sleeve pipe and preparation method thereof |
| CN107325408A (en) * | 2017-08-23 | 2017-11-07 | 安徽国泰印务有限公司 | A kind of flame retardant plastics packaging material |
| CN107353508A (en) * | 2017-08-23 | 2017-11-17 | 安徽国泰印务有限公司 | A kind of wear-resistant uvioresistant line polypropylene film packaging material |
| CN110467767A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of fire-retardant B1 grades of cable of 0.6/1kV |
| CN110577697A (en) * | 2019-09-20 | 2019-12-17 | 江苏德威新材料股份有限公司 | UVLED light attenuation irradiation resistant crosslinked polyethylene insulation master batch and preparation method and application thereof |
| CN111410784A (en) * | 2020-04-03 | 2020-07-14 | 江苏鼎尚电子材料股份有限公司 | Heat-shrinkable sleeve free of foaming when heated and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463160A (en) * | 2009-01-12 | 2009-06-24 | 上海雅祥新型高分子材料有限公司 | Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation thereof |
| CN102161793A (en) * | 2011-03-07 | 2011-08-24 | 黑龙江省润特科技有限公司 | Ultraviolet deep-crosslinked expansion flame-retardant polyolefine cable material, and preparation method of insulating or jacket layer thereof |
| CN102585345A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Oil-proof low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation method and application thereof |
| CN102731895A (en) * | 2012-07-06 | 2012-10-17 | 深圳市沃尔核材股份有限公司 | 1E-grade K1 type halogen-free flame retardant material for nuclear power plants and application thereof |
| CN102766293A (en) * | 2011-08-16 | 2012-11-07 | 深圳市沃尔核材股份有限公司 | Radiation cross-linked low-smoke halogen-free red phosphorus-free flame retardant material and its application |
| CN103087395A (en) * | 2013-02-27 | 2013-05-08 | 四川省原子能研究院 | Grade-1E K2-type radiation cross-linked halogen-free flame-retardant cable material for nuclear power plant and preparation method thereof |
| CN103483670A (en) * | 2013-10-10 | 2014-01-01 | 长园集团股份有限公司 | 150 DEG C high-flame-retardant halogen-free red phosphorus-free modified material |
-
2015
- 2015-12-03 CN CN201510876414.5A patent/CN105400057A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463160A (en) * | 2009-01-12 | 2009-06-24 | 上海雅祥新型高分子材料有限公司 | Halogen-free flame-retardant polymer sandwich layer material for fireproofing plastic-aluminum plate and preparation thereof |
| CN102161793A (en) * | 2011-03-07 | 2011-08-24 | 黑龙江省润特科技有限公司 | Ultraviolet deep-crosslinked expansion flame-retardant polyolefine cable material, and preparation method of insulating or jacket layer thereof |
| CN102766293A (en) * | 2011-08-16 | 2012-11-07 | 深圳市沃尔核材股份有限公司 | Radiation cross-linked low-smoke halogen-free red phosphorus-free flame retardant material and its application |
| CN102585345A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Oil-proof low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation method and application thereof |
| CN102731895A (en) * | 2012-07-06 | 2012-10-17 | 深圳市沃尔核材股份有限公司 | 1E-grade K1 type halogen-free flame retardant material for nuclear power plants and application thereof |
| CN103087395A (en) * | 2013-02-27 | 2013-05-08 | 四川省原子能研究院 | Grade-1E K2-type radiation cross-linked halogen-free flame-retardant cable material for nuclear power plant and preparation method thereof |
| CN103483670A (en) * | 2013-10-10 | 2014-01-01 | 长园集团股份有限公司 | 150 DEG C high-flame-retardant halogen-free red phosphorus-free modified material |
Non-Patent Citations (1)
| Title |
|---|
| 张师军 等: "《聚乙烯树脂及其应用》", 30 November 2011, 化学工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496755A (en) * | 2016-10-13 | 2017-03-15 | 苏州沃尔兴电子科技有限公司 | A kind of high convergency multiplying power fire retardant thermal shrinkage sleeve pipe and preparation method thereof |
| CN107325408A (en) * | 2017-08-23 | 2017-11-07 | 安徽国泰印务有限公司 | A kind of flame retardant plastics packaging material |
| CN107353508A (en) * | 2017-08-23 | 2017-11-17 | 安徽国泰印务有限公司 | A kind of wear-resistant uvioresistant line polypropylene film packaging material |
| CN110467767A (en) * | 2019-07-25 | 2019-11-19 | 安徽电缆股份有限公司 | A kind of fire-retardant B1 grades of cable of 0.6/1kV |
| CN110577697A (en) * | 2019-09-20 | 2019-12-17 | 江苏德威新材料股份有限公司 | UVLED light attenuation irradiation resistant crosslinked polyethylene insulation master batch and preparation method and application thereof |
| CN111410784A (en) * | 2020-04-03 | 2020-07-14 | 江苏鼎尚电子材料股份有限公司 | Heat-shrinkable sleeve free of foaming when heated and preparation method thereof |
| CN113024927A (en) * | 2021-03-24 | 2021-06-25 | 中科英华长春高技术有限公司 | Nuclear power 1E-grade K1-class heat-shrinkable cable accessory material and preparation method thereof |
| CN113024927B (en) * | 2021-03-24 | 2022-08-16 | 中科英华长春高技术有限公司 | Nuclear power 1E-grade K1-class heat-shrinkable cable accessory material and preparation method thereof |
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