CN104725833A - Yellowing-resistant halogen-free flame retardant thermoplastic polyurethane elastomer cable rubber material and preparation method thereof - Google Patents
Yellowing-resistant halogen-free flame retardant thermoplastic polyurethane elastomer cable rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a yellowing-resistant halogen-free flame retardant thermoplastic polyurethane elastomer cable rubber material. The rubber material is prepared from the following components in parts by weight: 60-80 parts of polyether type polyurethane elastomer, 0.01-5 parts of yellowing resistant agent, 5-15 parts of phosphorus based flame retardant, 10-30 parts of nitrogen series flame retardant and 0.01-3 parts of antioxidant. The invention also provides a preparation method of the yellowing-resistant halogen-free flame retardant thermoplastic polyurethane elastomer cable rubber material. A wire prepared by use of the yellowing-resistant halogen-free flame retardant thermoplastic polyurethane elastomer cable rubber material is excellent in yellowing resistance, has delta YI of less than 1.5, and is at a zero non-decoloring grade; the rubber material is environment-friendly and excellent in fire resistance; the oxygen index of the rubber material is greater than 30, and therefore, the rubber material is a first grade flame retardant rubber material; the insulating material of the wire is excellent in various properties, outstanding in hydrolysis resistance; and besides, the flame resistance of the material passes the VW-1 test.
Description
Technical field
The present invention relates to wire cable insulating, sheath technical field, particularly relate to a kind of color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material.
Background technology
Polyurethane Thermoplastic Elastomer various aspects of performance is excellent, and wear-resisting, oil resistant, the performance such as low temperature resistant are given prominence to, and apply more and more extensive in recent years.In electric wire field, Polyurethane Thermoplastic Elastomer cable occupies a tiny space in the environment that ask for something is harsh or special.Also there are some defects in Polyurethane Thermoplastic Elastomer itself, such as: the easy xanthochromia of polyurethane material of light color, affects appearance property; Oxygen index is only 18, belongs to inflammable material; Some urethane facile hydrolysiss, to be not suitable for being used in high humidity or water surrounding etc.All face heat at the cable of new-energy automobile field and mine, marine field application, photoaging causes xanthochromia problem, there is very high requirement in a lot of field to environmental protection and fire-retardant problem simultaneously.
Therefore, develop the polyurethane elastomer that a kind of color inhibition halogen-free flameproof has excellent hydrolytic resistance capability simultaneously and become necessity.
Summary of the invention
The object of the invention is to for the problems referred to above, provide a kind of heatproof 125 DEG C of halogen-free stibium-free high flame retardant cable materials.
For reaching above-mentioned purpose, color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material provided by the present invention, by weight, contains:
Polyether(poly)urethane elastomerics 60-80 part;
Color inhibition agent 0.01-5 part;
Phosphorus flame retardant 5-15 part;
Nitrogenated flame retardant 10-30 part;
Oxidation inhibitor 0.01-3 part;
Lubricant 0-3 part.
Preferably, described color inhibition agent is benzophenone type ultraviolet absorption agent.
Preferably, described phosphorus flame retardant is organic hypophosphite based flame retardant.
Preferably, described nitrogenated flame retardant is melamine cyanurate.
Preferably, described oxidation inhibitor is the constituent of phosphite ester kind antioxidant, sulphur ester antioxidant.
Preferably, described lubricant is N, N '-ethylene bis stearamide (EBS), silicone masterbatch, one or several in organosilicon.
The present invention also provides the preparation method of color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material, comprise the following steps: after the 60-80 part polyurethane elastomer in color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material is thoroughly dried with 90 ° of C × 6h, with the color inhibition agent 0.01-5 part in cable sizing material, phosphorus flame retardant 5-15 part, nitrogenated flame retardant 10-30 part, oxidation inhibitor 0.01-3 part, lubricant 0-3 part one coexists stirrer for mixing, feeding machine is poured into after mixing, and start twin screw granulation operations, twin screw rate of feeding is 10-30 r/min, screw speed is 10-35 r/min, conveying and melt zone temperature are 100-130 ° of C, mixing section and exhaust section temperature are 120-150 ° of C, homogenizing zone temperature 130-150 ° C, halogen-free environment-friendly flame-proof polyurethane elastomer cable material is obtained through water-cooled and high speed dicing machine after extruding.
The wire rod anti-yellowing property prepared of color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material of the present invention is better, and △ YI is less than 1.5, be 0 grade without variable color grade; Sizing material environmental protection and flame retardant properties is good, oxygen index is greater than 30, and belong to one-level difficulty combustion sizing material, the insulating material various aspects of performance of wire rod is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
Embodiment
For the research of anti-yellowing polyurethane elastomer material, CN103709729A have employed a certain amount of acrylate modifier with excellent weather resistance to improve its anti-yellowing property; CN1517392A adopts a kind of composition of the ultraviolet absorbers, benzotriazole category ultraviolet absorbers and the antioxidant that comprise formamidine to improve the anti-yellowing property of polyurethane elastomer, and anti-yellowing property all improves.
For the research of halogen-free flameproof performance, CN101166782 is with phosphoric acid ester/phosphonic acid ester for fire retardant, and flame retardant properties is better, and sizing material is by V-0 flame retardant rating; CN101058669 then have employed the halogen-free expansion fire retardant of organo-silicon coupling agent process, and system coordinates with titanium dioxide etc., and product flame retardant properties is better, and by VW-1 flame retardant test, the flame-retardant system for TPU proposes a new thinking; CN102120875A is then on the basis of CN101058669, and adopt the mixture of phosphonate and nitrogenous compound as fire retardant, system has coordinated the materials such as viscosity modifier, obtains the good sizing material of flame retardant properties equally.
Above-mentioned disclosed technology is compared, there is following feature in the present invention: color inhibition aspect, using benzophenone type ultraviolet absorption agent as color inhibition agent, be aided with phosphite ester kind antioxidant, the component of sulphur ester antioxidant is oxidation inhibitor, taken into account the requirement of heat-resisting xanthochromia, fast light xanthochromia simultaneously; Halogen-free flameproof aspect, combines the feature advantage of phosphorus flame retardant and nitrogenated flame retardant, has outstanding flame retardant properties; The present invention can meet the requirement of color inhibition and halogen-free flameproof simultaneously.
By describing technology contents of the present invention, formula rate in detail, being realized object and effect, be explained in detail below in conjunction with embodiment.
Below describing present embodiment adopts color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material of the present invention to produce several specific embodiments of wire rod, unless otherwise indicated, all numbers all by weight:
embodiment 1
Be that the polyether(poly)urethane elastomerics (TPU-85A) of 85A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A85(77 part), UV-9(0.5 part), melamine aminuria cyanate (11 parts), diethyl sodium hypophosphite (6 parts), antioxidant 1010 (3 parts), silicone masterbatch (2.5 parts).Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 12rpm and 18rpm.I 120 ± 5 DEG C, district, 130 ± 5 DEG C, machine barrel II district, 140 ± 5 DEG C, machine barrel III district, 145 ± 5 DEG C, machine barrel IV district, head and 135 ± 5 DEG C, mould, dicing machine pelletizing speed is 220rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 50 extruder extrusion wire rod, design external diameter is 2.73mm, and wall thickness is 0.78mm.Sizing material and wire rod are numbered TPU-1.Full performance test result is as shown in table 1 below:
Table 1 TPU-1 full performance test table
by test result is known above, sizing material anti-yellowing property is better, and △ YI is less than 1.5, be 0 grade without variable color grade; Sizing material environmental protection and flame retardant properties is good, oxygen index is 30, belongs to one-level difficulty combustion sizing material.The insulating material various aspects of performance of wire rod is excellent, and anti-yellowing property is better, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 2
Be that the polyether(poly)urethane elastomerics (TPU-78A) of 78A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A78 66 parts, UV-531 5 parts, melamine cyanurate 14 parts, 2-carboxyethyl phenyl sodium hypophosphite 14 parts, antioxidant BHT 0.3 part, irgasfos 168 0.2 part, organosilicon 0.5 part.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 20rpm and 28rpm.I 110 ± 5 DEG C, district, 120 ± 5 DEG C, machine barrel II district, 130 ± 5 DEG C, machine barrel III district, 140 ± 5 DEG C, machine barrel IV district, head and 135 ± 5 DEG C, mould, dicing machine pelletizing speed is 310rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 60 extruder extrusion single-core cable sheath, the outside diameter of cable is 3.6mm, and jacket thickness is 0.8mm, and internal layer is crosslinked PE insulated line.Sizing material and cable number are TPU-2.Full performance test result is as shown in table 2 below:
Table 2 TPU-2 full performance test table
By test result is known above, sizing material anti-yellowing property is better, and △ YI is less than 1.5, be 0 grade without variable color grade, sizing material anti-yellowing property is better; Sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 33, belongs to one-level difficulty combustion sizing material.The sheath material various aspects of performance of cable is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 3
Be that the polyether(poly)urethane elastomerics (TPU-90A) of 90A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A90 78 parts, DOBP 3 parts, melamine cyanurate 8 parts, phenyl hypo-aluminum orthophosphate 10 parts, antioxidant 1010 0.2 part, irgasfos 168 0.2 part, silicone masterbatch 0.6 part, female 2 parts of EVA based black.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 115 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 40 extruder extrusion electric wire, design external diameter is 2.82mm, and insulation thickness is 0.8mm.Sizing material and electric wire are numbered TPU-3.Full performance test result is as shown in table 3 below:
Table 3 TPU-3 full performance test table
By test result is known above, sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 31, belongs to one-level difficulty combustion sizing material.Electric wire material various aspects of performance is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 4
Be that the polyether(poly)urethane elastomerics (TPU-85A) of 85A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A85 55 parts, melamine cyanurate 28 parts, ethyl hypo-aluminum orthophosphate 14 parts, antioxidant 1010 0.3 part, irgasfos 168 0.2 part, silicone masterbatch 0.5 part, female 2 parts of EVA based black.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 115 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 50 extruder extrusion electric wire, design external diameter is 3.96mm, and insulation thickness is 0.8mm.Sizing material and electric wire are numbered TPU-4.Full performance test result is as shown in table 4 below:
Table 4 TPU-4 full performance test table
By test result is known above, sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 35, belongs to one-level difficulty combustion sizing material.Electric wire material various aspects of performance is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 5
Be that the polyether(poly)urethane elastomerics (TPU-80A) of 80A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A80 65 parts, DOBP 2 parts, melamine cyanurate 21 parts, ethyl sodium hypophosphite 11 parts, antioxidant 1010 0.3 part, irgasfos 168 0.2 part, silicone masterbatch 0.5 part.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 125 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 50 extruder extrusion electric wire, design external diameter is 6.2mm, and insulation thickness is 1.6mm.Sizing material and electric wire are numbered TPU-5.Full performance test result is as shown in table 5 below:
Table 5 TPU-5 full performance test table
By test result is known above, △ YI is less than 1.5, be 0 grade without variable color grade, anti-yellowing property give prominence to; Sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 32, belongs to one-level difficulty combustion sizing material.Electric wire material various aspects of performance is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 5-2
Be that the polyether(poly)urethane elastomerics (TPU-80A) of 80A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A80 65 parts, DOBP 2 parts, melamine cyanurate 21 parts, ethyl sodium hypophosphite 11 parts, antioxidant 1010 0.3 part, irgasfos 168 0.2 part, silicone masterbatch 0.5 part.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 125 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then sizing material is used for simple performance test, and following test is carried out under identical condition with embodiment 5 simultaneously.
Table 5-2 TPU-5.2 performance test table
By test result is known above, there are 2 grades of light discolourations in sizing material, △ YI is 3.2, shows that sizing material itself is without ageing resistance.
embodiment 6
Be that the polyether(poly)urethane elastomerics (TPU-80A) of 80A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A80(65 part), DOBP(0.2 part), melamine cyanurate (22 parts), methylol sodium hypophosphite (12 parts), antioxidant 1010 (0.3 part), irgasfos 168 (0.2 part), silicone masterbatch (0.3 part).Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 125 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 50 extruder extrusion single-core cable sheath, design external diameter is 5.2, and sheath wall thickness is 0.8mm, and primary insulation is crosslinked PE material.Sizing material and cable number are TPU-6.Full performance test result is as shown in table 6 below:
Table 6 TPU-6 full performance test table
By test result is known above, △ YI is less than 1.5, be 0 grade without variable color grade, anti-yellowing property give prominence to; Sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 32, belongs to one-level difficulty combustion sizing material.Electric wire material various aspects of performance is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
embodiment 7
Be that the polyether(poly)urethane elastomerics (TPU-80A) of 80A is dried in the blast drier of 90 ° of C by hardness, take following materials in material bag: TPU-A80 65 parts, DOBP 2.5 parts, melamine cyanurate 21 parts, ethyl hypo-aluminum orthophosphate 11 parts, antioxidant 1010 0.3 part, irgasfos 168 0.2 part.Material is transferred to stirring and evenly mixing in stirrer and is placed on little twin screw feeding bucket, start twin-screw extrusion operation.Rate of feeding and twin screw speed is regulated to be respectively 11rpm and 18rpm.I 125 ± 5 DEG C, district, 125 ± 5 DEG C, machine barrel II district, 135 ± 5 DEG C, machine barrel III district, 150 ± 5 DEG C, machine barrel IV district, head and 145 ± 5 DEG C, mould, dicing machine pelletizing speed is 210rpm.After pelletizing completes, blast drier sizing material being placed in 90 ° of C dries 6h, then in φ 50 extruder extrusion single-core cable sheath, design external diameter is 5.2, and sheath wall thickness is 0.8mm, and primary insulation is crosslinked PE material.Sizing material and cable number are TPU-6.Full performance test result is as shown in table 6 below:
Table 7 TPU-6 full performance test table
By test result is known above, △ YI is less than 1.5, be 0 grade without variable color grade, anti-yellowing property give prominence to; Sizing material halogen-free environmental and flame retardant properties is good, oxygen index is 31.5, belongs to one-level difficulty combustion sizing material.Electric wire material various aspects of performance is excellent, and anti-hydrolytic performance is given prominence to, and is fire-retardantly tested by VW-1.
The present invention is not limited to above-mentioned embodiment, and those skilled in the art also can make multiple change accordingly, but to be anyly equal to the present invention or similar change all should be encompassed in the scope of the claims in the present invention.
Claims (7)
1. a color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material, is characterized in that, by weight, contains:
Polyether(poly)urethane elastomerics 60-80 part;
Color inhibition agent 0.01-5 part;
Phosphorus flame retardant 5-15 part;
Nitrogenated flame retardant 10-30 part;
Oxidation inhibitor 0.01-3 part;
Lubricant 0-3 part.
2. the color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material as described in right 1, is characterized in that: described color inhibition agent is benzophenone type ultraviolet absorption agent.
3. the color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material as described in right 1, is characterized in that: described phosphorus flame retardant is organic hypophosphite based flame retardant.
4. the color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material as described in right 1, is characterized in that: described nitrogenated flame retardant is melamine cyanurate.
5. the color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material as described in right 1, is characterized in that: described oxidation inhibitor is the constituent of phosphite ester kind antioxidant, sulphur ester antioxidant.
6. the color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material as described in right 1, is characterized in that: described lubricant is N, N '-ethylene bis stearamide (EBS), silicone masterbatch, one or several in organosilicon.
7. the preparation method of a color inhibition halogen-free fire retardation thermoplastic polyurethane elastomerics cable sizing material, comprise the following steps: after 60-80 part polyurethane elastomer is thoroughly dried with 90 ° of C × 6h, with the color inhibition agent 0.01-5 part in cable sizing material, phosphorus flame retardant 5-15 part, nitrogenated flame retardant 10-30 part, oxidation inhibitor 0.01-3 part, lubricant 0-3 part one coexists stirrer for mixing, feeding machine is poured into after mixing, and start twin screw granulation operations, twin screw rate of feeding is 10-30 r/min, screw speed is 10-35 r/min, conveying and melt zone temperature are 100-130 ° of C, mixing section and exhaust section temperature are 120-150 ° of C, homogenizing zone temperature 130-150 ° C, halogen-free environment-friendly flame-proof polyurethane elastomer cable material is obtained through water-cooled and high speed dicing machine after extruding.
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| CN112724656A (en) * | 2020-12-28 | 2021-04-30 | 福建汇得新材料有限公司 | Halogen-free flame-retardant TPU cable material and preparation method and application thereof |
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| CN112724656A (en) * | 2020-12-28 | 2021-04-30 | 福建汇得新材料有限公司 | Halogen-free flame-retardant TPU cable material and preparation method and application thereof |
| CN112920592A (en) * | 2021-01-28 | 2021-06-08 | 杭州卓时新材料有限公司 | Electric wire material and preparation method thereof |
| CN113234315A (en) * | 2021-05-12 | 2021-08-10 | 东莞市通锦新材料科技有限公司 | Flame-retardant yellowing-resistant TPU cable material and preparation method and application thereof |
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Application publication date: 20150624 |