CN104479339B - Non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material and preparation method thereof - Google Patents
Non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material and preparation method thereof Download PDFInfo
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- CN104479339B CN104479339B CN201410800416.1A CN201410800416A CN104479339B CN 104479339 B CN104479339 B CN 104479339B CN 201410800416 A CN201410800416 A CN 201410800416A CN 104479339 B CN104479339 B CN 104479339B
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Abstract
The invention belongs to Thermoplastic polyurethane elastomer material technical field, more particularly to a kind of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material is by weight percentage, composed of the following components：70% ~ 85% thermoplastic polyurethane elastomer；10% ~ 28% Halogen nitrogen phosphorus type flame retardant；1% ~ 5% smoke suppressant；0.1% ~ 1% antioxidant；0.1% ~ 1% lubricant.The non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material prepared using the present invention life smoke in burning is low, has excellent flame retardant property and excellent mechanical property, can be used as the use of low-smoke halogen-free inflaming-retarding cable covering material.In addition, the invention also discloses a kind of preparation methods of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material.
Description
Technical field
The invention belongs to Thermoplastic polyurethane elastomer material technical field more particularly to a kind of non-halogen flame-proof smoke-restraining thermoplastics
Property polyurethane elastomer cable material and preparation method thereof.
Background technology
Cable is conveying electric energy, transmits information and the various motors of manufacture, instrument, instrument, realizes electromagnetic energy conversion institute not
The basic equipment that can lack.However, traditional polyvinyl chloride cable is in use since aging is easy to happen catching fire,
Cause fire, and generation is a large amount of toxic and has corrosive smog.Therefore, it is necessary to select low-fume non-bittern flame-retardant electrical wire electric
Cable material reduces the danger of fire, reduces the generation of fire, protects the safety of people's life and property.
Thermoplastic polyurethane elastomer have good comprehensive physical performance, such as its with excellent wear-resisting property,
Have higher elasticity, high intensity and elongation at break, higher biocompatibility, damping force stronger and good under high rigidity
The excellent properties such as oil resistant and resistant to many solvent.Therefore, thermoplastic polyurethane elastomer be widely used in injection, extrusion, calendering and
The processing methods such as solution resin are dissolved into, are the plastic materials that plastic cement processer is commonly used, feature makes it that can also answer
For in electric wire industry.
Thermoplastic polyurethane elastomer is as similar in other most of high molecular materials, and inflammable and easy molten drop generates a large amount of
Smog.Therefore it is also required to carry out flame retardant treatment to thermoplastic polyurethane elastomer.Halogen containing flame-retardant in burning due to that can release
Toxic, corrosive gas is released, to the mankind and environment there is great hidden danger, is had been unable to meet current increasingly harsh
Environmental requirement.Halogen-free fire retardation thermoplastic polyurethane product is mainly by adding inorganic combustion inhibitor to obtain flame retardant property.Such as Europe
Patent EP 0389768, which is disclosed, a kind of utilizing the compound resistances such as Mg (OH) 2 and Al (OH) 3, melamine aminuria cyanic acid and phosphate
The method that combustion agent carrys out flame-proof thermoplastic polyurethane.Such method haves the shortcomings that amount of flame-retardant agent is big, can lead to thermoplastic poly ammonia
Ester mechanical property declines to a great extent, its original flexibility of body that follows the string, obtained product is especially caused to be only used for noting
Plastic, it is difficult to be used for extrusion moulding.
Novel nitrogen phosphorus type flame retardant have many advantages, such as additive amount is low, flame retarding efficiency is high, easily at charcoal and not molten drop.Such as patent US
4,324,835 propose the dilatancy resistance for using ammonium polyphosphate, inorganic acid to be mixed with pentaerythrite as thermoplastic urethane foam
Agent is fired, JP 01/40588 describes a kind of method that ammonium polyphosphate and zinc borate apply flame-proof thermoplastic polyurethane together.Such as
Chinese patent 200910144076.0 reports core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material, can reduce resistance
The shortcomings that firing the additive amount of agent, and resistance to molten drop is good, while improving the poor water resistance of flame retardant composite material containing ammonium polyphosphate, enhancing
The compatibility of fire retardant and polyurethane elastomer.
However such thermoplastic polyurethane elastomer flame-retardant system, there is no special smoke suppressing effects, generally require use
Smoke suppressants and the expansion type flame retardants such as molybdenum compound, iron compound, metal oxide, magnesium zinc complexes, zinc aluminate and zinc stannate
It is used in compounding.Research shows that (2,013 142 531-538 of Materials Chemistry and Physics) is graphene-supported
Cobalt oxide and nickel oxide, can not only be greatly reduced peak heat release and improve fire safety, moreover it is possible to significantly reduce material
The release of smoke density and imflammable gas.So far, have no multiple with nitrogen phosphorus type flame retardant using graphene-supported smoke suppressant
Report with flame-retardant smoke inhibition thermoplastic polyurethane elastomer.
Invention content
It is an object of the present invention to：For the deficiency of current flame retardant thermoplastic polyurethane elastomer cable material, carry
Go out a kind of environmental protection, safety, non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material, the non-halogen flame-proof smoke-restraining thermoplastic poly
It is low that smoke is given birth to when urethane elasticity volumetric combustion, and there is excellent flame retardant property and excellent mechanical property, can be used as low smoke and zero halogen
Flame retardant cable covering material uses.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material, by weight percentage, by following components
Composition：
Thermoplastic polyurethane elastomer 70% ~ 85%；
Halogen nitrogen phosphorus type flame retardant 10% ~ 28%；
Smoke suppressant 1% ~ 5%；
Antioxidant 0.1% ~ 1%；
Lubricant 0.1% ~ 1%.
As a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention, by weight
Percentages are measured, it is composed of the following components：
Thermoplastic polyurethane elastomer 75% ~ 80%；
Halogen nitrogen phosphorus type flame retardant 15% ~ 20%；
Smoke suppressant 2% ~ 4%；
Antioxidant 0.1% ~ 1%；
Lubricant 0.1% ~ 1%.
It is described as a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Thermoplastic polyurethane elastomer be in thermoplastic polyester type polyurethane elastomer and thermoplastic polyether urethane elastomer extremely
Few one kind.
It is described as a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Halogen nitrogen phosphorus type flame retardant is Silica hydrogel microencapsulation ammonium polyphosphate, melamine resin microencapsulation ammonium polyphosphate, the micro- glue of cellulose
At least one of encapsulated ammonium polyphosphate and epoxy resin micro-capsule ammonium polyphosphate.Halogen nitrogen phosphorus type flame retardant is selected, i.e.,
Environmental-friendly microcapsule Phosphorus-nitrogen flame retardant so that fire-retardant thermoplastic polyurethane elastomer cable material flame retarding efficiency is high and does not melt
The advantages that drop；In addition the bittern-free phosphorous-nitrogen type fire retardant that the present invention selects has the advantages that water-tolerant so that fire-retardant thermoplasticity
Polyurethane elastomer cable material has excellent durability and weatherability.
It is described as a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Smoke suppressant is at least one of graphene-supported zinc hydroxyl stannate and graphene-supported zinc stannate.Graphene is as novel two
Among dimension sheet layer material is dispersed in thermoplastic polyurethane elastomer with nm regime, graphene sheet layer blocking effect significantly reduces material
The heat release and total heat release of material, improve the fire safety of material；The smoke restraining object matter loaded on graphene is uniformly dispersed in
Among thermoplastic polyurethane elastomer, so as to give full play to the smoke suppressing effect of smoke suppressant, it is burned to reduce polyurethane material
The poison gas discharged in journey.Smoke restraining object matter can play the role of fire-retardant synergistic with novel phosphor nitrogen fire retardant, can obviously carry
High fire-retardance effect, so as to reduce the usage amount of fire retardant in polyurethane system so that flame retardant thermoplastic polyurethane elastomer
The mechanical performance of cable material is improved.
It is described as a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters（Antioxidant 1010）, 4,4 '-thiobis
（6- tertiary butyl -3- methylphenols）（Antioxidant 300）, dilauryl thiodipropionate（Anti-oxidant DLTP）, pentaerythrite four（3-
Lauryl thiopropionate）（Antioxidant S4P）With three [2.4- di-tert-butyl-phenyls] phosphite esters（Irgasfos 168）In at least
It is a kind of.
It is described as a kind of improvement of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Lubricant is at least one of zinc stearate, paraffin and PE waxes.
The advantageous effect of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention is：Using
Non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material prepared by the present invention life smoke in burning is low, has excellent
Flame retardant property and excellent mechanical property, can be used as low-smoke halogen-free inflaming-retarding cable covering material use.
It is another object of the present invention to additionally provide a kind of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable
1% ~ 5% suppression cigarette will be added by weight percentage in the preparation method of material in 70% ~ 85% thermoplastic polyurethane elastomer
Agent, be then kneaded in mixer or extruder be subsequently added into uniform 10% ~ 28% Halogen nitrogen phosphorus type flame retardant, 0.1% ~
1% antioxidant and 0.1% ~ 1% lubricant are mixed, and are granulated into non-halogen flame-proof smoke-restraining heat at 160 ~ 190 DEG C after mixing
Plastic polyurethane elastomer cable material.Non-halogen flame-proof smoke-restraining thermoplastic poly can be rapidly prepared by above-mentioned preparation method
Urethane elastomer cable material, it is important that the preparation method is simple and practical.
One of preparation method as non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material of the present invention
Kind is improved, and the temperature being kneaded in mixer or extruder is 160 ~ 190 DEG C.
Specific implementation mode
With reference to embodiment, the invention will be further described：
1% stone will be added by weight percentage in embodiment 1 in 70.8% thermoplastic polyester type polyurethane elastomer
Black alkene loads zinc hydroxyl stannate, is then kneaded in mixer to uniform, the temperature of the mixing is 160 DEG C, is subsequently added into 28%
Silica hydrogel microencapsulation ammonium polyphosphate, 0.1% the zinc stearate of antioxidant S4P and 0.1% mixed, exist after mixing
160 DEG C are granulated into non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material.
Testing result shows：The drawing of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material manufactured in the present embodiment
It is 35.5MPa to stretch intensity, and elongation at break 680%, oxygen index (OI) 29.5%, testing vertical flammability passes through V0 grades of UL-94, cigarette
Density is 210.
3% graphite will be added by weight percentage in embodiment 2 in 85% thermoplastic polyether urethane elastomer
Alkene loads zinc stannate, is then kneaded in an extruder to uniform, and the temperature of the mixing is 190 DEG C, is subsequently added into 10% Silica hydrogel
Microencapsulation ammonium polyphosphate, 1% antioxidant 1010 and 1% PE waxes are mixed, and are granulated into Halogen at 190 DEG C after mixing
Flame-retardant smoke inhibition thermoplastic polyurethane elastomer cable material.
Testing result shows：The drawing of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material manufactured in the present embodiment
It is 25.8MPa to stretch intensity, and elongation at break 610%, oxygen index (OI) 32.5%, testing vertical flammability passes through V0 grades of UL-94, cigarette
Density is 150.
Embodiment 3, by weight percentage, by 25% thermoplastic polyester type polyurethane elastomer and 50% thermoplastic polyether
2% graphene-supported zinc stannate and 2% graphene-supported zinc hydroxyl stannate are added in the mixture of type polyurethane elastomer
Then mixture is kneaded in an extruder to uniform, the temperature of the mixing is 170 DEG C, is subsequently added into 10% cellulose microcapsules
Change ammonium polyphosphate, 0.4% antioxidant 300 and 0.6% paraffin to be mixed, is granulated into Halogen resistance at 170 DEG C after mixing
Combustion suppression cigarette thermoplastic polyurethane elastomer cable material.
Testing result shows：The drawing of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material manufactured in the present embodiment
It is 29.8MPa to stretch intensity, and elongation at break 630%, oxygen index (OI) 35.5%, testing vertical flammability passes through V0 grades of UL-94, cigarette
Density is 200.
Embodiment 4, by weight percentage, by 50% thermoplastic polyester type polyurethane elastomer and 30% thermoplastic polyether
3% graphene-supported zinc hydroxyl stannate is added in the mixture of type polyurethane elastomer, is then kneaded in an extruder to equal
Even, the temperature of the mixing is 180 DEG C, be subsequently added into 15% epoxy resin micro-capsule ammonium polyphosphate, 1% anti-oxidant DLTP and
1% paraffin is mixed, and is granulated into non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material at 180 DEG C after mixing
Material.
Testing result shows：The drawing of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material manufactured in the present embodiment
It is 28.8MPa to stretch intensity, and elongation at break 620%, oxygen index (OI) 34.5%, testing vertical flammability passes through V0 grades of UL-94, cigarette
Density is 199.
2% graphene will be added by weight percentage in embodiment 5 in 76% thermoplastic polyester type polyurethane elastomer
Zinc hydroxyl stannate is loaded, is then kneaded in an extruder to uniform, the temperature of the mixing is 165 DEG C, is subsequently added into 20% fiber
Plain microencapsulation ammonium polyphosphate, 1% irgasfos 168 and 1% paraffin are mixed, and are granulated into nothing at 165 DEG C after mixing
Halogen flame-retardant smoke inhibition thermoplastic polyurethane elastomer cable material.
Testing result shows：The drawing of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material manufactured in the present embodiment
It is 34.8MPa to stretch intensity, and elongation at break 635%, oxygen index (OI) 36.5%, testing vertical flammability passes through V0 grades of UL-94, cigarette
Density is 210.
The smoke density assay method of fire-retardant product is in the various embodiments described above：It is tested using the NBS smoke boxes in the U.S., wherein surveying
Test-object standard is ASATM E662；Tensile strength and elongation at break testing standard are ASTM D412；Oxygen index (OI) testing standard is
ASTM D2863；Testing vertical flammability testing standard is ASTM D3801.
The above, only preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, it is any ripe
Those skilled in the art are known in the technical scope of present disclosure, the change or replacement that can be readily occurred in should all be contained
Lid is within protection scope of the present invention.Therefore, the scope of protection of the invention shall be subject to the scope of protection specified in the patent claim.
Claims (7)
1. a kind of non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material, which is characterized in that by weight percentage, by
Following components forms：
Thermoplastic polyurethane elastomer 70% ~ 85%；
Halogen nitrogen phosphorus type flame retardant 10% ~ 28%；
Smoke suppressant 1% ~ 5%；
Antioxidant 0.1% ~ 1%；
Lubricant 0.1% ~ 1%；
The smoke suppressant is at least one of graphene-supported zinc hydroxyl stannate and graphene-supported zinc stannate；
The Halogen nitrogen phosphorus type flame retardant is Silica hydrogel microencapsulation ammonium polyphosphate, melamine resin microencapsulation ammonium polyphosphate, fibre
Dimension plain at least one of microencapsulation ammonium polyphosphate and epoxy resin micro-capsule ammonium polyphosphate.
2. according to the non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material described in claim 1, which is characterized in that
By weight percentage, composed of the following components：
Thermoplastic polyurethane elastomer 75% ~ 80%；
Halogen nitrogen phosphorus type flame retardant 15% ~ 20%；
Smoke suppressant 2% ~ 4%；
Antioxidant 0.1% ~ 1%；
Lubricant 0.1% ~ 1%.
3. according to the non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material described in claim 1, it is characterised in that：
The thermoplastic polyurethane elastomer is in thermoplastic polyester type polyurethane elastomer and thermoplastic polyether urethane elastomer
At least one.
4. according to the non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material described in claim 1, it is characterised in that：
The antioxidant is four [β-(3,5- di-t-butyl -4- hydroxy phenyls) propionic acid] pentaerythritol esters, 4,4 '-thiobis（6-
Tertiary butyl -3- methylphenols）, dilauryl thiodipropionate, pentaerythrite four（3- lauryl thiopropionates）With three [2,
At least one of 4- di-tert-butyl-phenyls] phosphite ester.
5. according to the non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material described in claim 1, it is characterised in that：
The lubricant is at least one of zinc stearate, paraffin and PE waxes.
6. a kind of preparation of claim 1 ~ 5 any one of them non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material
Method, it is characterised in that：By weight percentage, smoke suppressant will be added in thermoplastic polyurethane elastomer, then in mixer
Or be kneaded to uniform in extruder, Halogen nitrogen phosphorus type flame retardant, antioxidant and the lubricant being subsequently added into are mixed, mixing
Non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material is granulated at 160 ~ 190 DEG C after uniformly.
7. according to the preparation method of the non-halogen flame-proof smoke-restraining thermoplastic polyurethane elastomer cable material described in claim 6,
It is characterized in that：The temperature being kneaded in mixer or extruder is 160 ~ 190 DEG C.
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Families Citing this family (14)
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| CN104893248B (en) * | 2015-05-27 | 2017-01-11 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN106046683B (en) * | 2016-07-07 | 2018-05-15 | 西华大学 | Low-smoke and flame retardant polymer composite and preparation method thereof |
| CN106633789A (en) * | 2016-09-30 | 2017-05-10 | 无锡市明盛强力风机有限公司 | Halogen-free flame retardant TPU film and preparation method thereof |
| CN107383310B (en) * | 2017-07-24 | 2020-05-12 | 应瑶琪 | Preparation method of phosphated flame-retardant polyurethane material |
| CN108504285A (en) * | 2018-04-09 | 2018-09-07 | 徐冬 | A kind of preparation method of food packaging fire-retardant bubble chamber film |
| CN108976588B (en) * | 2018-08-02 | 2020-11-03 | 福州大学 | Flame-retardant antistatic EVA foam composite material and preparation method thereof |
| CN109251713A (en) * | 2018-08-10 | 2019-01-22 | 苏州郎旭志远科技有限公司 | A kind of high viscosity flame-retardant polyurethane sealant and preparation method thereof |
| CN109988411B (en) * | 2019-03-13 | 2021-07-16 | 台州博尔特塑胶电子有限公司 | Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof |
| CN111218102A (en) * | 2020-02-24 | 2020-06-02 | 顺德职业技术学院 | Polyurethane elastomer containing P-C-N symbiotic flame retardant and preparation method thereof |
| CN111218103A (en) * | 2020-03-18 | 2020-06-02 | 博硕科技(江西)有限公司 | Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof |
| CN112048168B (en) * | 2020-08-25 | 2022-09-02 | 南通大学 | High-performance TPU composite material for automobile foot pad and preparation method thereof |
| CN112164496A (en) * | 2020-09-24 | 2021-01-01 | 广东电网有限责任公司 | Cable structure |
| CN113416406A (en) * | 2021-07-27 | 2021-09-21 | 中广核高新核材科技（苏州）有限公司 | TPU fuel inhibitor and preparation method thereof |
| CN114456580A (en) * | 2022-02-23 | 2022-05-10 | 上海申远高温线有限公司 | Low-smoke halogen-free thermoplastic elastomer fire-resistant cable material and production process |
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| CN103436001A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Low-smoke halogen-free flame retardant thermoplastic polyurethane elastomer for cable and preparation method thereof |
| CN103599769B (en) * | 2013-11-21 | 2015-04-15 | 福州大学 | ZnSn (OH)6 nanometer cubic particle/graphene sandwich structure compound light catalyst |
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Denomination of invention: Halogen-free flame-retardant smoke-suppressing thermoplastic polyurethane elastomer cable material and preparation method thereof Effective date of registration: 20200506 Granted publication date: 20180828 Pledgee: Dongguan branch of Bank of Dongguan Co., Ltd Pledgor: ANGREEN (DONGGUAN) NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: Y2020980001969 |