CN102295835B - 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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- CN102295835B CN102295835B CN 201010209537 CN201010209537A CN102295835B CN 102295835 B CN102295835 B CN 102295835B CN 201010209537 CN201010209537 CN 201010209537 CN 201010209537 A CN201010209537 A CN 201010209537A CN 102295835 B CN102295835 B CN 102295835B
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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 and application thereof.
Background technology
Polyurethane Thermoplastic Elastomer is come out the history of many decades, to develop in recent years rapidly, the performance of Polyurethane Thermoplastic Elastomer is very superior, oxygen, ozone and radiation etc. there are enough resistivities, have very high tensile strength and elongation at break, have simultaneously good wear resistance, oil-proofness and winter hardiness, these performances make Polyurethane Thermoplastic Elastomer as CABLE MATERIALS, in the environment of ask for something harshness, occupy a tiny space.But Polyurethane Thermoplastic Elastomer also comes with some shortcomings, and for example the oxygen index of 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 again flame retardant resistance.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 and application thereof 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 smoke suppressant 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; The Halogen smoke suppressant is 10-15 part, and modifier is 5-15 part.
Described urethane is selected from the urethane that contains phenyl or contains the urethane etc. of carbonate group, such 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 (such as FR-600, FR-700), three hydroxyl hexyl cyanide urates and red phosphorus etc.
Described Halogen smoke suppressant 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-butadiene-styrene copolymer etc.
Described oxidation inhibitor can be selected from Hinered phenols antioxidant.Such as antioxidant KY-1076 (β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid), KY-1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) etc.
Described processing aid is selected from metal soap lubricant such as calcium stearate, Magnesium Stearate and Zinic stearas etc.
Described anti ultraviolet agent is selected from UV-531 (Octabenzone), UV-9 (ESCALOL 567) etc.
The preparation method of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material of the present invention is: take urethane as base material, it is suitably toughness reinforcing to base material to add by weight ratio modifier, add processing aid and improve the materials processing performance, add oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.
Better, adopting the twin screw extruder extruding pelletization, the twin screw extruder temperature setting 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, mainly be applicable to voltage rating 1KV and the following wind power generation equipment that the halogen-free flameproof requirement arranged is used electric wire, and earphone cord, charger line, supply lead, military project line, nuclear power line, vehicle wire etc. that the halogen-free flameproof requirement is arranged.
Compare with corresponding product with prior art, the invention has the advantages that: the wider processing temperature of extruding, 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 for restriction protection scope of the present invention.
Embodiment 1
Urethane, halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, have the prescription as shown in table 1, 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-butadiene-styrene copolymer | 10 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method: with polyurethane base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.The twin screw extruder temperature setting 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 smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, have the prescription as shown in table 3, performance is as shown in table 4.
Table 3
| Material name | Weight part |
| Urethane WHT-7185 | 55 |
| FR-600 | 15 |
| Zinc borate | 15 |
| Acrylonitrile-butadiene-styrene copolymer | 15 |
| Magnesium Stearate | 0.2 |
| KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method: with polyurethane base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.The twin screw extruder temperature setting 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 smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, have the prescription as shown in table 5, 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: with polyurethane base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.The twin screw extruder temperature setting 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 smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, have the prescription as shown in table 7, 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-butadiene-styrene copolymer | 5 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1010 | 0.2 |
| UV-531 | 0.2 |
Preparation method: with polyurethane base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.The twin screw extruder temperature setting 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 smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, have the prescription as shown in table 9, 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-butadiene-styrene copolymer | 10 |
| Magnesium Stearate | 0.2 |
| Antioxidant KY-1076 | 0.2 |
| UV-531 | 0.2 |
Preparation method: with polyurethane base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.The twin screw extruder temperature setting 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 (9)
1. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material, adopt to comprise that the raw material of following component and weight part makes:
Described urethane is selected from one or more in the urethane that contains phenyl or contain carbonate group;
Described halogen-free flame retardants is selected from one or more in phosphoric acid ester, three hydroxyl hexyl cyanide urates or the red phosphorus;
Described Halogen smoke suppressant is selected from one or more in magnesium hydroxide, zinc borate, aluminum oxide or the titanium dioxide;
Described modifier is selected from one or more in ethylene vinyl acetate, ethylene acrylic acid co polymer or the acrylonitrile-butadiene-styrene copolymer;
Described halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material, made by following steps: take urethane as base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.
2. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in 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 processing aid is selected from the metal soap lubricant.
4. halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as claimed in claim 3 is characterized in that described metal soap lubricant is selected from calcium stearate, Magnesium Stearate or Zinic stearas.
5. 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.
6. 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.
7. such as the preparation method of halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the arbitrary claim of claim 1-6, comprise the following steps: take urethane as base material, add by weight ratio halogen-free flame retardants, Halogen smoke suppressant, modifier, processing aid, oxidation inhibitor and anti ultraviolet agent, after mixing, through double-screw extruding pelletizing.
8. the preparation method of halogen-free flameproof ardent hope based polyurethane elastomer sheathing material as claimed in claim 7, it is characterized in that, described twin screw extruder temperature setting 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 ℃.
As halogen-free fire retardation thermoplastic polyurethane elastomer sheathing material as described in the arbitrary claim of claim 1-6 for the preparation of 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, supply lead, military project line, nuclear power line or vehicle wire that halogen-free flameproof requires arranged.
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| CN 201010209537 CN102295835B (en) | 2010-06-24 | 2010-06-24 | Zero-halogen flame-retardant thermoplastic polyurethane elastomer sheath material and preparation as well as application thereof |
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| CN110144112B (en) * | 2019-05-13 | 2021-11-23 | 浙江万马聚力新材料科技有限公司 | Halogen-free cable material, preparation method thereof and cable containing halogen-free cable material |
| KR102098542B1 (en) * | 2019-09-09 | 2020-04-07 | 엘에스전선 주식회사 | Composition for sheath of cable comprising thermoplastic polyurethane resin and cable having a sheath layer formed from the same |
| KR102461768B1 (en) * | 2019-09-09 | 2022-10-31 | 엘에스전선 주식회사 | Cable having a sheath layer formed from composition for sheath of cable comprising thermoplastic polyurethane resin |
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