CN103044758A - Thermoplastic water-resistant low-smoke halogen-free flame retardant cable material and manufacturing method thereof - Google Patents
Thermoplastic water-resistant low-smoke halogen-free flame retardant cable material and manufacturing method thereof Download PDFInfo
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- CN103044758A CN103044758A CN201210563752XA CN201210563752A CN103044758A CN 103044758 A CN103044758 A CN 103044758A CN 201210563752X A CN201210563752X A CN 201210563752XA CN 201210563752 A CN201210563752 A CN 201210563752A CN 103044758 A CN103044758 A CN 103044758A
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Abstract
The invention discloses a thermoplastic water-resistant low-smoke halogen-free flame retardant cable material which is prepared from the following raw materials in part by weight: 40-100 parts of ethylene-ethylene vinyl acetate copolymer, 10-60 parts of linear low-density polyethylene, 15-25 parts of macromolecular compatibilizer, 120-160 parts of inorganic filler, 2-4 parts of surface treating agent, 0.5-1 part of antioxidant, 1.5-2 parts of carbon black masterbatch and 2-5 parts of processing aid. The manufacturing method of the cable material comprises the following steps of matrix resin blending and extrusion, inorganic filler pretreatment, extrusion granulation and the like. The thermoplastic water-resistant low-smoke halogen-free flame retardant cable material and the manufacturing method thereof have the characteristics and the advantages of excellent water resistance, heat resistance and mechanical performance, better toughness and bending resistance, better cracking resistance and flame retardant property, low density, low smoke, low toxicity and environment friendliness.
Description
Technical field
The present invention relates to the field of fireproofing cable material without halide, particularly the water-fast fireproofing cable material without halide of a kind of thermoplasticity and manufacture method thereof.
Background technology
The fire retardant material of domestic wires and cables industry mostly is the Halogen fire retardant material in the past, and this material combustion discharges a large amount of dense smokes and corrodibility halogenide, all can cause damage to human body and environment.And present many bittern-free flame-proof materials are adding a large amount of inorganic combustion inhibitors or other auxiliary agents also to have brought some problems when reaching fire-retardant purpose, and mechanical property is lower especially in use; Because suction causes mechanical property further to descend, volume specific resistance, breaking down field strength descend after making moist, and cracking, electric leakage had brought hidden danger to public safety during cable used.
Summary of the invention
One of technical problem to be solved by this invention is to provide a kind of thermoplasticity water-fast fireproofing cable material without halide for the existing problem of existing non-halogen flame-retardant cable, the water-fast fireproofing cable material without halide of this thermoplasticity has higher flame retardant effect, mechanical property and electric property preferably, and density is lower, water-fast, environmental friendliness, processing characteristics is good.
Two of technical problem to be solved by this invention is to provide the manufacture method of the water-fast fireproofing cable material without halide of above-mentioned thermoplasticity.
The water-fast fireproofing cable material without halide of a kind of thermoplasticity as the present invention's the first invention is prepared from by following mass parts raw material:
40～100 parts of ethylene-vinyl acetate copolymers;
10～60 parts of linear low density polyethylenes;
15～25 parts of high molecular weight compatibilizers;
120～160 parts of mineral fillers;
2～4 parts of surface treatment agents;
0.5～1 part in oxidation inhibitor;
1.5～2 parts of black masterbatchs;
2～5 parts of processing aids;
Wherein:
In the described ethylene-vinyl acetate copolymer, the mass percentage content of its vinyl acetate is 20～40%, and melting index is 2～8g/min.
Described high molecular weight compatibilizer is one or both mixing in maleic anhydride graft terpolymer EP rubber, maleic anhydride grafted polyethylene, the maleated ethylene vinyl acetate copolyme.
Described mineral filler is one or both mixing or the three kinds of mixing in aluminium hydroxide, magnesium hydroxide, the kaolin.
Described surface treatment agent is one or both mixing in stearic acid, Aluminate, titanic acid ester or the silane coupling agent.
Described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 4, in 4 '-thiobis (6-tertiary butyl meta-cresol), β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid, Tyox B or thio-2 acid two (18) ester one or both and two or more mixing.
Described processing aid is a kind of in polyethylene wax or the ethylene bis stearic acid amide.
A second aspect of the present invention is the preparation method of the water-fast fireproofing cable material without halide of thermoplasticity, is prepared from by following steps:
(1) manufacturing of matrix resin: ethylene-vinyl acetate copolymer, linear low density polyethylene added in the high-speed mixer with oxidation inhibitor mix, then obtain matrix resin through the twin screw extruder extruding pelletization; The temperature of twin screw extruder barrel is: 90～100 ℃ of feeding sections, 95～105 ℃ of transportation sections, 105～125 ℃ of fluxing zones, 100～120 ℃ of heads;
(2) pre-treatment of mineral filler: mineral filler is added high-speed mixer stir, the treatment time is 1～2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm; Add afterwards surface treatment agent and continue to stir, the treatment time is 1～2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm.Obtain pretreated mineral filler;
Together put into the abundant mixing that high-speed mixer carries out 5min after the pretreated mineral filler of the matrix resin that (3) step (1) is prepared, step (2) preparation and high molecular weight compatibilizer, black masterbatch and the processing aid batching; Then add Banbury mixer and carry out banburying, temperature is 110～120 ℃, and the time is 5～10min; Put into single screw extrusion machine after the banburying and carry out extruding pelletization; The temperature of single screw extrusion machine barrel is: 100～110 ℃ of feeding sections, 110～120 ℃ of transportation sections, 115～130 ℃ of fluxing zones, 110～125 ℃ of heads.
The present invention has used high molecular weight compatibilizer, the surface treatment agent through selection, adopts ripe base-material, mineral filler treatment process, obtains the water-fast fireproofing cable material without halide of a kind of thermoplasticity.Compared with prior art, the present invention possesses following characteristics and advantages simultaneously: higher mechanical property (tensile strength reaches 12MPa); Flame retardant properties preferably; Low density (is lower than 1.39g/cm
3), low cigarette, low toxicity, water-fast, anti-cracking, environmental friendliness; Good processing characteristics.
Embodiment
The embodiments of the invention formula for raw stock sees Table 1.
Fireproofing cable material without halide Example formulations that table 1 thermoplasticity is water-fast (umber)
Wherein:
The high molecular weight compatibilizer that embodiment 1 adopts is maleic anhydride grafted polyethylene; The surface treatment agent that adopts is aluminate coupling agent; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; The processing aid that adopts is ethylene bis stearic acid amide.
The high molecular weight compatibilizer that embodiment 2 adopts is maleic anhydride grafted polyethylene; The surface treatment agent that adopts is aluminate coupling agent; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and Tyox Bs (proportioning is 5:7); The processing aid that adopts is polyethylene wax.
The high molecular weight compatibilizer that embodiment 3 adopts is maleic anhydride grafted polyethylene; The surface treatment agent that adopts is silane coupling agent; The oxidation inhibitor that adopts is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid; The processing aid that adopts is polyethylene wax.
The high molecular weight compatibilizer that embodiment 4 adopts is maleated ethylene vinyl acetate copolyme; The surface treatment agent that adopts is silane coupling agent; The oxidation inhibitor that adopts is β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid; The processing aid that adopts is polyethylene wax.
The high molecular weight compatibilizer that embodiment 5 adopts is maleated ethylene vinyl acetate copolyme; The surface treatment agent that adopts is silane coupling agent; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and Tyox Bs (proportioning is 5:7); The processing aid that adopts is polyethylene wax.
The high molecular weight compatibilizer that embodiment 6 adopts is the maleic anhydride graft terpolymer EP rubber; The surface treatment agent that adopts is stearic acid; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; The processing aid that adopts is ethylene bis stearic acid amide.
Embodiment 1～6 adopts following manufacture method:
(1) manufacturing of matrix resin: ethylene-vinyl acetate copolymer, linear low density polyethylene added in the high-speed mixer with oxidation inhibitor mix, then obtain matrix resin through the twin screw extruder extruding pelletization; The temperature of twin screw extruder barrel is: 90 ℃ of feeding sections, 105 ℃ of transportation sections, 115 ℃ of fluxing zones, 100 ℃ of heads;
(2) pre-treatment of mineral filler: mineral filler is added high-speed mixer stir, the treatment time is 1.5h, and treatment temp is 100 ℃, and rotating speed is 1440rpm; Add afterwards surface treatment agent and continue to stir, the treatment time is 2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm.Obtain pretreated mineral filler;
(3) with the matrix resin of step (1) preparation, pretreated mineral filler and high molecular weight compatibilizer, black masterbatch and the processing aid batching of step (2) preparation, quota is 60kg, together puts into the abundant mixing that high-speed mixer carries out 5min; Then add Banbury mixer and carry out banburying, temperature is 110～120 ℃, and the time is 5～10min; Put into after the banburying with single screw extrusion machine and carry out extruding pelletization.The temperature of screw rod is: 105 ℃ of feeding sections, 115 ℃ of transportation sections, 130 ℃ of fluxing zones, 120 ℃ of heads.
The CABLE MATERIALS performance of embodiment 1～6 sees Table 2.
The performance of each embodiment CABLE MATERIALS of table 2
Wherein the performance of embodiment 3 sees Table 3 in addition.
The performance of table 3 embodiment 3
| Sequence number | Performance | Unit | Embodiment 3 |
| 1 | Tensile strength | MPa | 12.9 |
| 2 | Elongation at break | % | 213 |
| 3 | The air heat ageing test (100 ℃, 168h) | / | / |
| 3.1 | The tensile strength retention rate | % | 95 |
| 3.2 | Reserved elongation at break | % | 99 |
| 4 | Water immersion test (23 ℃, 24h) | / | / |
| 4.1 | Print quality rate of increase | % | 0.01 |
| 4.2 | The tensile strength retention rate | % | 98 |
| 4.3 | Reserved elongation at break | % | 105 |
| 5 | Water immersion test (23 ℃, 168h) | / | / |
| 5.1 | Print quality rate of increase | % | 0.01 |
| 5.2 | The tensile strength retention rate | % | 102 |
| 5.3 | Reserved elongation at break | % | 105 |
| 6 | Melting index | g/10min | 10.2 |
| 7 | Density | 3g/cm | 1.39 |
| 8 | Hot split test (130 ℃, 1h) | / | By |
| 9 | Low temperature brittleness (25 ℃) | Failure number | 0/30 |
| 10 | Volume specific resistance (20 ℃) | Ω·m | 1.1*10 12 |
| 11 | Dielectric strength | MV/m | 29 |
| 12 | Smoke density (nonflame) | / | 148 |
| 13 | Oxygen index | % | 35 |
| 14 | Halogen acid gas content | mg/g | 0 |
| 15 | PH value | / | 5.6 |
| 16 | Specific conductivity | μs/mm | 1 |
| 17 | Poison exponent | / | 1.2 |
The formula for raw stock of the Comparative Examples of embodiment 1 is identical with embodiment 1, and the formula for raw stock of Comparative Examples sees Table 4.
The Comparative Examples prescription (umber) of table 4 thermoplasticity is water-fast fireproofing cable material without halide embodiment 1
Wherein:
The resin that Comparative Examples 1 adopts is without pretreated resin; The mineral filler of adopting is the pretreated mineral filler of process; The high molecular weight compatibilizer that adopts is maleic anhydride grafted polyethylene; The surface treatment agent that adopts is aluminate coupling agent; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; The processing aid that adopts is ethylene bis stearic acid amide.
Comparative Examples 1 adopts following manufacture method:
(1) pre-treatment of mineral filler: mineral filler is added high-speed mixer stir, the treatment time is 1.5h, and treatment temp is 100 ℃, and rotating speed is 1440rpm; Add afterwards surface treatment agent and continue to stir, the treatment time is 2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm.Obtain pretreated mineral filler;
(2) with pretreated mineral filler and oxidation inhibitor, high molecular weight compatibilizer, black masterbatch and the processing aid batching of ethylene-vinyl acetate copolymer, linear low density polyethylene, step (1) preparation, together put into the abundant mixing that high-speed mixer carries out 5min; Then add Banbury mixer and carry out banburying, temperature is 110～120 ℃, and the time is 5～10min; Put into after the banburying with single screw extrusion machine and carry out extruding pelletization.The temperature of screw rod is: 105 ℃ of feeding sections, 115 ℃ of transportation sections, 130 ℃ of fluxing zones, 120 ℃ of heads.
The resin that Comparative Examples 2 adopts is the pretreated matrix resin of process; The mineral filler of adopting is not pretreated mineral filler; The high molecular weight compatibilizer that adopts is maleic anhydride grafted polyethylene; The surface treatment agent that adopts is aluminate coupling agent; The oxidation inhibitor that adopts is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; The processing aid that adopts is ethylene bis stearic acid amide.
Comparative Examples 2 adopts following manufacture method:
(1) manufacturing of matrix resin: ethylene-vinyl acetate copolymer, linear low density polyethylene added in the high-speed mixer with oxidation inhibitor mix, then obtain matrix resin through the twin screw extruder extruding pelletization; The temperature of twin screw extruder barrel is: 90 ℃ of feeding sections, 105 ℃ of transportation sections, 115 ℃ of fluxing zones, 100 ℃ of heads;
(2) with matrix resin and mineral filler, surface treatment agent, high molecular weight compatibilizer, black masterbatch and the processing aid batching of step (1) preparation, together put into the abundant mixing that high-speed mixer carries out 5min; Then add Banbury mixer and carry out banburying, temperature is 110～120 ℃, and the time is 5～10min; Put into after the banburying with single screw extrusion machine and carry out extruding pelletization.The temperature of screw rod is: 105 ℃ of feeding sections, 115 ℃ of transportation sections, 130 ℃ of fluxing zones, 120 ℃ of heads.
Comparative Examples 1,2 CABLE MATERIALS performance see Table 5.
The performance of each Comparative Examples CABLE MATERIALS of table 5
Claims (8)
1. the water-fast fireproofing cable material without halide of thermoplasticity is characterized in that, is prepared from by following mass parts raw material:
40～100 parts of ethylene-vinyl acetate copolymers;
10～60 parts of linear low density polyethylenes;
15～25 parts of high molecular weight compatibilizers;
120～160 parts of mineral fillers;
2～4 parts of surface treatment agents;
0.5～1 part in oxidation inhibitor;
1.5～2 parts of black masterbatchs;
2～5 parts of processing aids.
2. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1 is characterized in that, in the described ethylene-vinyl acetate copolymer, the mass percentage content of its vinyl acetate is 20～40%, and melting index is 2～8g/min.
3. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1, it is characterized in that described high molecular weight compatibilizer is one or both mixing in maleic anhydride graft terpolymer EP rubber, maleic anhydride grafted polyethylene, the maleated ethylene vinyl acetate copolyme.
4. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1 is characterized in that, described mineral filler is one or both mixing or the three kinds of mixing in aluminium hydroxide, magnesium hydroxide, the kaolin.
5. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1 is characterized in that, described surface treatment agent is one or both mixing in stearic acid, Aluminate, titanic acid ester or the silane coupling agent.
6. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1, it is characterized in that, described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 4, in 4 '-thiobis (6-tertiary butyl meta-cresol), β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid, Tyox B or thio-2 acid two (18) ester one or both and two or more mixing.
7. the water-fast fireproofing cable material without halide of thermoplasticity as claimed in claim 1 is characterized in that, described processing aid is a kind of in polyethylene wax or the ethylene bis stearic acid amide.
8. the preparation method of the water-fast fireproofing cable material without halide of the described thermoplasticity of each claim of claim 1 to 7 is characterized in that, is prepared from by following steps:
(1) manufacturing of matrix resin: ethylene-vinyl acetate copolymer, linear low density polyethylene added in the high-speed mixer with oxidation inhibitor mix, then obtain matrix resin through the twin screw extruder extruding pelletization; The temperature of twin screw extruder barrel is: 90～100 ℃ of feeding sections, 95～105 ℃ of transportation sections, 105～125 ℃ of fluxing zones, 100～120 ℃ of heads;
(2) pre-treatment of mineral filler: mineral filler is added high-speed mixer stir, the treatment time is 1～2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm; Add afterwards surface treatment agent and continue to stir, the treatment time is 1～2h, and treatment temp is 100 ℃, and rotating speed is 1440rpm.Obtain pretreated mineral filler;
Together put into the abundant mixing that high-speed mixer carries out 5min after the pretreated mineral filler of the matrix resin that (3) step (1) is prepared, step (2) preparation and high molecular weight compatibilizer, black masterbatch and the processing aid batching; Then add Banbury mixer and carry out banburying, temperature is 110～120 ℃, and the time is 5～10min; Put into single screw extrusion machine after the banburying and carry out extruding pelletization; The temperature of single screw extrusion machine barrel is: 100～110 ℃ of feeding sections, 110～120 ℃ of transportation sections, 115～130 ℃ of fluxing zones, 110～125 ℃ of heads.
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| CN103387707A (en) * | 2013-07-22 | 2013-11-13 | 常熟市辛庄镇前进五金厂 | Flame-retardant polyethylene cable material |
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| CN103571009B (en) * | 2013-09-30 | 2016-04-13 | 芜湖航天特种电缆厂 | Fireproofing cable material without halide |
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