CN102295835A - Zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material and preparation as well as application thereof - Google Patents
Zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material and preparation as well as application thereof Download PDFInfo
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- CN102295835A CN102295835A CN 201010209537 CN201010209537A CN102295835A CN 102295835 A CN102295835 A CN 102295835A CN 201010209537 CN201010209537 CN 201010209537 CN 201010209537 A CN201010209537 A CN 201010209537A CN 102295835 A CN102295835 A CN 102295835A
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Abstract
The invention discloses a zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material and a preparation method thereof. The zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material is prepared from the following raw material components in parts by weight: 50-80 parts of polyurethane, 10-30 parts of zero-halogen flame retardant, 10-20 parts of zero-halogen smoke suppressant, 5-20 parts of processing modifier, 0.2+/-0.05 part of processing auxiliary agent, 0.2+/-0.05 part of antioxidant and 0.2+/-0.05 part of ultraviolet resistant. Compared with the prior art, the zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material prepared by the invention has the advantages of wider processing temperature range, ultrahigh physical and mechanical properties and flame retardant property of UL-94 and V-0 level.
Description
Technical field
The present invention relates to a kind of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material and preparation thereof and application.
Background technology
Polyurethane Thermoplastic Elastomer is come out the history of many decades, be to develop in recent years rapidly, the performance of Polyurethane Thermoplastic Elastomer is very superior, oxygen, ozone and radiation etc. all there are enough resistivities, have very high tensile strength and elongation at break, have good wear resistance, oil-proofness and winter hardiness simultaneously, these performances make Polyurethane Thermoplastic Elastomer as CABLE MATERIALS, in the ask for something rigorous environment, occupy a tiny space.But Polyurethane Thermoplastic Elastomer also comes with some shortcomings, and the oxygen index of for example narrow processing temperature, fancy price and polyurethane elastomer itself is 18 only, belongs to inflammable material.Because the singularity of the industry for the Polyurethane Thermoplastic Elastomer material, requires to have flame retardant resistance again.Common flame resistance polyurethane elastomer sheathing material mostly adopts halogen containing flame-retardant to obtain flame retardant resistance.But public environmentalist more and more payes attention to environment protection in recent years, especially pays close attention to the non-halogen development of wires and cables industry.So producing the halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material becomes social progress, the direction of industry development.
Summary of the invention
The technical issues that need to address of the present invention are to overcome defective of the prior art, and a kind of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material and preparation thereof and application are provided.
A kind of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material, adopt to comprise that the raw material of following component and weight part makes:
Urethane 50-80 part
Halogen-free flame retardants 10-30 part
Halogen presses down fumicants 10-20 part
Modifier 5-20 part
0.2 ± 0.05 part of processing aid
0.2 ± 0.05 part in oxidation inhibitor
0.2 ± 0.05 part of anti ultraviolet agent
Preferably, in the above-mentioned raw materials, urethane is 55-60 part; Halogen-free flame retardants is 15-20 part; It is 10-15 part that Halogen presses down fumicants, and modifier is 5-15 part.
Described urethane is selected from the urethane that contains phenyl or contains urethane of carbonate group etc., as ER-85A, WHT-7185, WHT-7180, WHT-7190 (the Yantai Wan Hua WHT-71 of company series) etc.
Described halogen-free flame retardants is selected from phosphoric acid ester (as FR-600, FR-700), three hydroxyl hexyl cyanide urates and red phosphorus etc.
Described Halogen presses down fumicants and is selected from magnesium hydroxide, zinc borate, aluminum oxide and titanium dioxide etc.
Described modifier is selected from ethylene vinyl acetate, ethylene acrylic acid co polymer and acrylonitrile-styrene-butadienecopolymer etc.
Described oxidation inhibitor can be selected from Hinered phenols antioxidant.As antioxidant KY-1076 (β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid), KY-1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) etc.
Described processing aid is selected from metallic soap series lubricant agent such as calcium stearate, Magnesium Stearate and Zinic stearas etc.
Described anti ultraviolet agent is selected from UV-531 (Octabenzone), UV-9 (2-hydroxyl-4-methoxy benzophenone) etc.
The preparation method of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material of the present invention is: be base material with urethane, it is suitably toughness reinforcing to base material to add modifier by weight ratio, add processing aid and improve the materials processing performance, add oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.
Preferable, adopting the twin screw extruder extruding pelletization, the twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould.
The halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material that the invention discloses, be applicable to that mainly voltage rating 1KV and the following wind power generation equipment that the halogen-free flameproof requirement arranged use electric wire, and earphone cord, charger line, supply lead, military project line, nuclear power line, automobile-used line etc. that the halogen-free flameproof requirement is arranged.
Compare with corresponding product with prior art, the invention has the advantages that: broad extrude processing temperature, superpower physical and mechanical properties, its flame retardant properties can reach UL-94, V-0 level level, every Specifeca tion speeification and corresponding external product are similar, and do not need the input of special cable wire rod extrusion equipment.
Embodiment
The invention will be further described below in conjunction with embodiment, should be understood that example is not to be used to limit protection scope of the present invention.
Embodiment 1
Urethane, halogen-free flame retardants, Halogen press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, and it is as shown in table 1 to have a prescription, and performance is as shown in table 2.
Table 1
| Material name | Weight part |
| Urethane WHT-7185 | 60 |
| Three hydroxyl hexyl cyanide urates | 15 |
| Zinc borate | 15 |
| Acrylonitrile-styrene-butadienecopolymer | 10 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method:, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing with polyurethane base material.The twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould.
Table 2
| Hardness (Shao Shi A) | 85 |
| Tensile strength (MPa) | 26 |
| Elongation at break (%) | 580 |
| Low temperature impact test | -56 ℃ are passed through |
| Oxygen index | 27 |
| The V-0 standard | By |
Embodiment 2
Urethane, halogen-free flame retardants, Halogen press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, and it is as shown in table 3 to have a prescription, and performance is as shown in table 4.
Table 3
| Material name | Weight part |
| Urethane WHT-7185 | 55 |
| FR-600 | 15 |
| Zinc borate | 15 |
| Acrylonitrile-styrene-butadienecopolymer | 15 |
| Magnesium Stearate | 0.2 |
| KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method:, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing with polyurethane base material.The twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould.
Table 4
| Hardness (Shao Shi A) | 87 |
| Tensile strength (MPa) | 25 |
| Elongation at break (%) | 450 |
| Low temperature impact test | -56 ℃ are passed through |
| Oxygen index | 28 |
| The V-0 standard | By |
Embodiment 3
Urethane, halogen-free flame retardants, Halogen press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, and it is as shown in table 5 to have a prescription, and performance is as shown in table 6.
Table 5
| Material name | Weight part |
| Urethane WHT-7185 | 60 |
| FR-600 | 20 |
| Magnesium hydroxide | 10 |
| Ethylene acrylic acid co polymer | 10 |
| Zinic stearas | 0.2 |
| KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method:, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing with polyurethane base material.The twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould
Table 6
| Hardness (Shao Shi A) | 87 |
| Tensile strength (MPa) | 26 |
| Elongation at break (%) | 560 |
| Low temperature impact test | -56 ℃ are passed through |
| Oxygen index | 27 |
| The V-0 standard | By |
Embodiment 4
Urethane, halogen-free flame retardants, Halogen press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, and it is as shown in table 7 to have a prescription, and performance is as shown in table 8.
Table 7
| Material name | Weight part |
| Urethane WHT-7180 | 60 |
| Three hydroxyl hexyl cyanide urates | 20 |
| Aluminum oxide | 15 |
| Acrylonitrile-styrene-butadienecopolymer | 5 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1010 | 0.2 |
| UV-531 | 0.2 |
Preparation method:, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing with polyurethane base material.The twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould.
Table 8
| Hardness (Shao Shi A) | 83 |
| Tensile strength (MPa) | 25 |
| Elongation at break (%) | 580 |
| Low temperature impact test | -56 ℃ are passed through |
| Oxygen index | 27 |
| The V-0 standard | By |
Embodiment 5
Urethane, halogen-free flame retardants, Halogen press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, and it is as shown in table 9 to have a prescription, and performance is as shown in table 10.
Table 9
| Material name | Weight part |
| Urethane WHT-7190 | 60 |
| Three hydroxyl hexyl cyanide urates | 15 |
| Magnesium hydroxide | 15 |
| Acrylonitrile-styrene-butadienecopolymer | 10 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method:, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing with polyurethane base material.The twin screw extruder temperature is set to: 140 ± 5 ℃ in machine barrel I district, 150 ± 5 ℃ in machine barrel II district, 160 ± 5 ℃ in machine barrel III district, 155 ± 5 ℃ in machine barrel IV district, 150 ± 5 ℃ on head and mould.
Table 10
| Hardness (Shao Shi A) | 90 |
| Tensile strength (MPa) | 29 |
| Elongation at break (%) | 550 |
| Low temperature impact test | -56 ℃ are passed through |
| Oxygen index | 26 |
| The V-0 standard | By |
Claims (13)
1. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material, adopt to comprise that the raw material of following component and weight part makes:
Urethane 50-80 part
Halogen-free flame retardants 10-30 part
Halogen presses down fumicants 10-20 part
Modifier 5-20 part
0.2 ± 0.05 part of processing aid
0.2 ± 0.05 part in oxidation inhibitor
0.2 ± 0.05 part of anti ultraviolet agent.
2. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material according to claim 1 is characterized in that described urethane is 55-60 part; Halogen-free flame retardants is 15-20 part; Modifier is 5-15 part.
3. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that, described urethane is selected from the urethane that contains phenyl or contains in the urethane of carbonate group one or more.
4. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that described halogen-free flame retardants is selected from one or more in phosphoric acid ester, three hydroxyl hexyl cyanide urates or the red phosphorus.
5. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that, described Halogen presses down fumicants and is selected from magnesium hydroxide, zinc borate, aluminum oxide or the titanium dioxide one or more.
6. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2, it is characterized in that described modifier is selected from one or more in ethylene vinyl acetate, ethylene acrylic acid co polymer or the acrylonitrile-styrene-butadienecopolymer.
7. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that described processing aid is selected from the metallic soap series lubricant agent.
8. as halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the claim 7, it is characterized in that described metallic soap series lubricant agent is selected from calcium stearate, Magnesium Stearate or Zinic stearas.
9. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that described oxidation inhibitor is selected from Hinered phenols antioxidant.
10. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 1 or 2 is characterized in that described anti ultraviolet agent is selected from UV-531 and UV-9.
11. preparation method as halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the arbitrary claim of claim 1-10, comprise the following steps: with urethane to be base material, add halogen-free flame retardants, Halogen by weight ratio and press down fumicants, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.
12. preparation method as halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the claim 11, it is characterized in that, described twin screw extruder temperature is set to: machine barrel I district 135-145 ℃, machine barrel II district 145-155 ℃, machine barrel III district 155-165 ℃, machine barrel IV district 150-160 ℃, head and mould 145-155 ℃.
13. as halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the arbitrary claim of claim 1-10 be used to prepare voltage rating 1KV and the following wind power generation equipment that the halogen-free flameproof requirement arranged with electric wire, the purposes of earphone cord, charger line, supply lead, military project line, nuclear power line or automobile-used line that halogen-free flameproof requires arranged.
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