CN102816427A - High-flame-retardance high-heat-resistance halogen-free flame-retardant thermoplastic polyurethane elastomer cable material and preparation method thereof - Google Patents
High-flame-retardance high-heat-resistance halogen-free flame-retardant thermoplastic polyurethane elastomer cable material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-flame-retardance high-heat-resistance halogen-free flame-retardant thermoplastic polyurethane elastomer cable material and a preparation method thereof, belonging to the field of halogen-free flame-retardant cable materials. The cable material is prepared from the following raw materials in percentage by weight: 20-50% of thermoplastic polyurethane elastomer, 15-40% of styrene elastomer, 3-8% of plasticizer, 20-30% of expansion flame retardant, 4-7% of flatting agent, 0.5-1% of lubricant, 0.5-1% of antioxidant and 1.5-3% of master batch. The thermoplastic polyurethane elastomer is a polyether-type thermoplastic polyurethane elastomer of which the hardness range is Shore A 60-90. The invention improves the problem of too narrow processing temperature region for the thermoplastic polyurethane elastomer cable material, and also improves the heat resistance of the cable material. The thermoplastic polyurethane elastomer, which is used as a base, is subjected to melt blending with the high-temperature-resistant material; and the novel expansion flame retardant which is nonmigratory in contact with water is used as the flame retardant of the base.
Description
Technical field:
The present invention relates to a kind of is the halogen-free flame-proof cable sheath material and the Insulation Material of matrix resin with the TPUE, refers more particularly to a kind of prescription of non-halogen flame-retardant cable.
Background technology:
The transmission that electric wire is applied to various electric energy and signal has had a lot of years, and therefore polymer materials becomes the first-selection of wire cable material base material because it is in light weight, electrical insulating property is good, be easy to moulding.Traditional P VC CABLE MATERIALS, owing to itself chloride element, so its flame retardant resistance is very good, is widely used in electric wire and cable material.But it generates a large amount of toxic gas and smog, serious harm people's safety of life and property when burning.The hydrogen chloride gas of emitting during the burning of PVC CABLE MATERIALS also can cause corrosion on Equipment, thereby causes " secondary pollution ".European Union had issued RoHS instruction and WEEE instruction in 2003, clearly proposed the application of restriction PVC CABLE MATERIALS.
At present, people adopt inorganic combustion inhibitor Mg (OH) usually
2And Al (OH)
3Polymer materials is carried out fire-retardant, Chinese patent publication number CN102140192A, low-smoke halogen-free polyolefin matrix material and preparation method thereof adopts Mg (OH)
2Carry out fire-retardant to polymkeric substance; Its flame retarding efficiency is low, needs to add just to reach higher fire-retardant requirement more than 60%, and this just greatly reduces the mechanical property of material; And the cable of preparation is very hard; Generally all at Shao A about 95, powder addition height causes processing characteristics obviously to descend to hardness, and energy consumption improves.Usually prepare non-halogen flame-retardant cable for the flame retarding efficiency that improves inorganic combustion inhibitor can add fire retarding synergist red phosphorus, the consumption of inorganic combustion inhibitor will reduce greatly like this, thereby can too not reduce the mechanical property of material.But because red phosphorus is prone to produce the phosphine gas of severe toxicity, and red phosphorus dust explosive, for this reason, red phosphorus must pass through surface treatment and could use safely and effectively.In addition, the inherent red-purple of red phosphorus own has limited the application of the CABLE MATERIALS that contains red phosphorus greatly.Chinese patent publication number CN 1557867A, the fire-retardant thing of Halogen nano flame retardant polyolefine adopts red phosphorus and nano-sized magnesium hydroxide to come flame-proof ethylene-vinyl acetate copolymer, and the composite materials property and the flame retardant properties of preparation are good.It is very big that but the fire-resistant cable material that contains red phosphorus all can be emitted the irritating smell and the amount of being fuming during in process of production with burning in large quantities, contaminate environment.Therefore the CABLE MATERIALS for preparing halogen-free environmental, softish, high flame retardant is imperative.
Expansion type flame retardant is that what to develop in recent years serves as the main fire retardant of forming with phosphorus, nitrogen, and this based flame retardant is when being heated, and surface energy forms one deck dense charcoal layer, plays heat insulation, oxygen barrier, presses down cigarette, can prevent molten drop again, has good flame retardancy.Therefore having obtained people pays close attention to widely.Chinese patent publication number CN101724194A, halogen-free intumescent flame-retardant composite adopts the fire-retardant linear low density polyethylene material of expansion type flame retardant, and the fire-retardant property of the matrix material of preparation is good.But adopt expanding fire retardant also to have some shortcomings, mainly be: (1) is prone to the moisture absorption, meets elutriation and goes out seriously.Meet water man-hour and be clamminess adding, apparent bad.And the problem that the chance elutriation goes out is not easy to solve very much; (2) expansion type flame retardant joins mechanical property, the especially tensile strength that reduces material in the polymer materials greatly, has only 9～11MPa.Therefore when selecting expansion type flame retardant, to carry out modification to it.
Polyurethane elastomer had both had the snappiness of rubber, had the HS of plastics again, can adopt the plastic thermoforming mode to process, and therefore was called TPUE (TPU) again.In addition; TPU also has excellent properties such as durometer level wide (adjustable), wear-resisting, oil resistant, recyclable utilization; Cause people's extensive concern, obtained very great development, become national defence, automobile, the energy, traffic, building, medical treatment and other industrial indispensable important materials.There is following difficult point in the technology of present halogen-free fire retardation thermoplastic polyurethane elastomer cable material: (1) processing temperature zone is very narrow, and is very responsive to temperature, is difficult to extrude; (2) thermotolerance of TPU material itself is relatively poor, and it is big to prepare high heat-stable CABLE MATERIALS difficulty; (3) TPU fusion drip phenomenon when burning is serious, and the flame retardant resistance that reach higher level is very very difficult; (4) the traditional expansion type flame retardant that adopts is met the water capacity and is prone to migration, and making the very glutinous hand in surface of material influences the goods feel.(5) material behavior of TPU is for extruding the surface for bright characteristic, and the client to require material surface mostly be cloudy surface, this product delustring is difficulty very.Chinese patent publication number CN101599314A; A kind of environmentally-friendly flame retardant thermoplastic polyurethane elastomer cable material, it is fire-retardant to adopt brominated flame-retardant that TPUE is carried out, and is the CABLE MATERIALS of non-Halogen requirement; And the CABLE MATERIALS temperature resistant grade of preparation is lower, and 80 ℃ of temperature resistant grades are only arranged.Whether flame retardant rating does not show yet can be through UL 1581 vertical combustion VW-1 test.
Summary of the invention:
In order to overcome the deficiency of prior art; Improve the narrow problem in thermoplastic polyurethane elastomer cable material processing temperature zone; Improve the resistance toheat of CABLE MATERIALS simultaneously, the present invention adopts TPUE as matrix, adopts high temperature material melt blending with it simultaneously; Adopt the fire retardant of the novel nonmigratory expansion type flame retardant of chance water, thereby a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material and preparation method thereof is provided as matrix.
The present invention realizes through following technical scheme.
A kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material is characterized in that its raw material by following percentage composition forms:
The matrix resin that the present invention adopts is the TPUE of polyether-type, and durometer level is Shao A 60～90.Because the hydrolytic stability of the TPUE of polyether-type is better than the polyester type, therefore adopt the TPUE of polyether-type.
The styrenic elastomerics that the present invention adopts is one or more a mixture of styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), styrene-ethylene-propylene-styrene segmented copolymer (SEPS), styrene-ethylene-(ethylene-propylene)-styrol copolymer (SEEPS).Adopt styrenic elastomerics and polyurethane elastomer blended, can greatly improve the mechanical property and the resistance toheat of CABLE MATERIALS.
The softening agent that the present invention adopts is one or more a mixture of industrial white oil, NO, Yellow Protopet 2A.
The fire retardant that the present invention adopts is novel halogen-free expansion fire retardant, in water, transport phenomena can not take place, and is one or more mixture of phosphorus flame retardant, nitrogen flame retardant and phosphorus-nitrogen flame retardant.
The matting agent that the present invention adopts is silicon-containing compound, especially silicon-dioxide etc.
The oxidation inhibitor that the present invention adopts is with four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) is primary antioxidant, three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168) is an auxiliary antioxidant, and the weight ratio of primary antioxidant and auxiliary antioxidant is 3:1.
The lubricant that the present invention adopts is one or more the mixture in Triple Pressed Stearic Acid, Zinic stearas, the amine hydroxybenzene.
The Masterbatch that the present invention adopts is one or more a blend of PE Masterbatch, PP Masterbatch.
In order to solve the narrow problem in TPUE processing temperature zone; Selected for use resistant to elevated temperatures styrenic elastomerics to carry out the melt blending modification with it; Thereby widened the work range of TPUE, the processing temperature zone is brought up to 40 ℃ by original 5 ℃, thereby makes thermoplastic elastomer process more easily; Extrusion is stable, obtains good cable outward appearance.
The present invention selects resistant to elevated temperatures styrenic elastomerics for use, except solving the narrow problem in processing temperature zone, makes also that simultaneously the resistance toheat of TPUE has a very significant increase, and temperature resistant grade is brought up to 105 ℃ by original 80 ℃.
The present invention selects for use styrenic elastomerics and TPUE to carry out blend, has improved the bright degree on the cable surface of preparation, has certain extinction effect, becomes half cloudy surface by original bright face, can reduce the consumption of matting agent.Therefore the mute light path degree on surface can need be adjusted by the client.
The expansion type flame retardant that is adopted among the present invention is novel halogen-free expansion fire retardant.It is not traditional ammonium phosphate type fire retardant, but organophosphate.The flame retarding efficiency of expansion type flame retardant is high, in combustion processes, can generate expansible dense char layer, drip phenomenon can not take place when making the thermoplastic polyurethane burning.And because the solubleness of this fire retardant in water is extremely low, so this based flame retardant adds in the polymkeric substance and can not meet the water transport phenomena.This meets the problem that elutriation goes out with regard to having solved traditional expansion type flame retardant.
The invention provides a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material, adopt novel expansion type flame retardant flame retardant thermoplastic polyurethane elastomer, make high performance non-halogen flame-retardant cable.The CABLE MATERIALS that is obtained has excellent flame-retardant and heat resistance.Print vertical combustion experiment 0.8mm thickness can reach the FV-0 grade, and oxygen index reaches 30～35%, and the wire rod of preparation can be tested through UL 1581 vertical combustion VW-1, and drip phenomenon can not take place.Temperature resistant grade can reach 105 ℃.Tensile strength is 20～25MPa, and elongation at break is 400～500%.Meeting water does not separate out; Can produce versicolor cable product with Masterbatch adapted together; And processing characteristics is excellent, and the cable of processing has good flexibility, wear resistance and oil-proofness, is mainly used in the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
The operational path of preparation Halogen thermoplastic polyurethane elastomer cable material is very simple, and operation can also utilize existing device of plastic processing easily.Operational path is: at first each component materials is weighed up by proportioning, the styrenic elastomerics is put into stirrer, through spray equipment spray softening agent, stirred 15 ~ 30 minutes; With stirring 15 ~ 30 minutes in TPUE, fire retardant, lubricant, matting agent, oxidation inhibitor and the Masterbatch adding stirrer, thorough mixing is even.The raw material that mixes is added in the twin screw extruder; Rate of feeding is 10 ~ 80rpm/min; Screw speed is 100 ~ 600rpm/min, and the length-to-diameter ratio of screw rod is 25 ~ 50, and processing temperature is 160 ~ 200 ℃; Preferred 180 ~ 200 ℃ of temperature obtains the thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
In order to guarantee the comparability of each performance perameter among the embodiment, the unified sample that thickness is 2mm, the mechanical property of pressing GB GB/T 1040-92 test compound material processed.The horizontal vertical combustion testing is tested according to GB GB/T 2408-1996, and the oxygen index test is tested according to GB GB 2406-93.
The invention has the advantages that:
(1) the present invention is owing to selected TPUE as matrix; Itself mechanical property is good, wear resistance is good, oil-proofness is excellent; After carrying out melt blending with the styrenic elastomerics, the CABLE MATERIALS thermotolerance of preparation improves, and temperature resistant grade is brought up to 105 ℃ by original 80 ℃; The processing temperature scope also broadens, and brings up to 40 ℃ by original 5 ℃.The bright mist degree that the styrenic elastomerics can be regulated cable surface again simultaneously can be served as matting agent and used, and reduces the consumption of matting agent.
(2) adopt novel expansion type flame retardant to come to carry out fire-retardant to polymkeric substance; Therefore the CABLE MATERIALS of preparation has higher flame retardant properties; Can be through UL 94 0.8mm FV-0 level estimates; And can drip phenomenon can not take place in the combustion processes through the VW-1 vertical combustion test of UL 1581 regulations.
(3) because TPUE has higher polarity; And the consistency that has equally between the polar expansion type flame retardant is fine; Mechanical property is excellent; Tensile strength can reach 20～25MPa, and elongation at break reaches 400～500%, and fire retardant is met the problem that water does not have migration yet simultaneously.
(4) through adding the styrenic elastomerics of softening agent and soft; Make that the CABLE MATERIALS flexibility of preparation is fine, hardness is at Shao A 70～90, and goods have outward appearance preferably; Carry out after the delustring through adding matting agent, the cable outward appearance of preparation can be adjusted to atomized surface effect.
(5) mechanical property of non-halogen flame-retardant cable of the present invention, flame retardant properties, resistance toheat are all apparently higher than the index request of halogen-free flame-retardant cable industry; Especially add after the styrenic elastomerics; The temperature resistant grade of goods is brought up to 105 ℃ by original 80 ℃, can use with sheath material or the Insulation Material done wear resistance, oil-proofness, the high temperature resistant and fire-retardant communication cable that has higher requirements, automobile cable, shipboard cable and computer peripheral cable.
Embodiment
With embodiment the inventive method is done further concrete detailed explanation below.
Each starting material among the embodiment can be chosen the related prods of each producer, and the present invention enumerates raw-material producer, but should not be construed as limitation of the present invention.
TPUE (TPU) is Bayer A.G's product, model 9385;
Styrenic elastomerics SEEPS 4055, Japanese Kuraray company produces;
Styrenic elastomerics SEBS G1651, U.S. section rise company and produce;
Styrenic elastomerics SEPS G1730, U.S. section rise company and produce;
Expansion type flame retardant is a Germany gram Lay benefactor department
Phosphor nitrogen combustion inhibitor, model is OP1312;
Industrial white oil is produced for limited-liability company of China Petrochemical Industry;
Matting agent silicon-dioxide is that Beijing space flight Saden powder body material technology ltd produces;
The lubricant siloxanes is that Dow Corning Corporation produces;
Oxidation inhibitor is 1010 and 168 of Albemarle Corporation;
Masterbatch is the PE Masterbatch, and Masterbatch company in Ningbo produces.
Embodiment 1:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 11.
The preparation method is following: take by weighing each component according to composition of raw materials; Earlier styrenic elastomerics (SEEPS) is added in the stirrer; Spray softening agent (industrial white oil); Stirred 30 minutes, again with TPU, novel phosphor nitrogen combustion inhibitor, silicon-dioxide, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
The CABLE MATERIALS of preparation is given as security line through giving as security the line machine, and the compression ratio of giving as security the line machine is 2.5:1, gives as security the line temperature and does; First section is 160 ℃, and second section is 170 ℃, and the 3rd section is 180 ℃, and the 4th section is 180 ℃; The 5th section is 190 ℃, and the 6th section is 190 ℃, processes electric wire; Wall thickness 0.6mm, the standard copper wire adopts 0.12 mm * 20, and each item results of property of test is as shown in table 2.Wherein hardness is carried out according to ASTM D2240 standard, reads 30 seconds hardness values afterwards.The tensile property of cable carries out according to UL 1581 standards, and draw speed is 500mm/min, test tensile strength and elongation at break.The VW-1 combustion experiment is tested according to UL 1581 standards.The oil resistant experiment is tested according to IEC 60811-2-1 standard.Weathering test is tested according to IEC 60811-1-2 standard.
Test result is shown in table 2 embodiment 1, and the result shows: the CABLE MATERIALS mechanical property of preparation is high, and good flame resistance can be through UL 1581 vertical combustion VW-1 test.Resistance toheat is high, can reach 105 ℃ of temperature resistant grades.Goods oil resistant, wear-resisting and cable is soft flexible, smooth surface and be mute light effect, place for some time after no fire retardant move, be suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Embodiment 2:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 12.
Preparing method and testing method are all with embodiment 1.
Compare embodiment 1, the content with SEEPS in the present embodiment improves, and test result is shown in table 2 embodiment 2; The result shows: after SEEPS content increased, the CABLE MATERIALS resistance toheat of preparation improved, and tensile strength has the decline than amplitude; Elongation at break rises, and good flame resistance can be through the test of VW-1 vertical combustion; The cable softness is flexible; Smooth surface and be mute light effect, place for some time after no fire retardant move, be suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Embodiment 3:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 13.
Preparing method and testing method are all with embodiment 1.
Compare embodiment 2, in the present embodiment content of SEEPS is brought up to 28%, the content of TPU is reduced to 30%; Flame retardant amount slightly increases, and test result is shown in table 2 embodiment 3, and the result shows: after the content of SEEPS brings up to 28%; The CABLE MATERIALS thermotolerance of preparation improves more obvious, and mechanical property remains unchanged basically, explains that the raising that SEEPS content increases resistance toheat has great role; And the CABLE MATERIALS good flame resistance of preparation, soft more, feel is fine; Oil resistant, wear-resisting, smooth surface and be mute light effect, place for some time after no fire retardant move, be suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Embodiment 4:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 14.
Preparing method and testing method are all with embodiment 1.
Compare embodiment 3, in the present embodiment content of SEEPS is brought up to 40%, the content of TPU is reduced to 20%; Flame retardant amount increases, and test result is shown in table 2 embodiment 4, and the result shows: after the content of SEEPS improves; The CABLE MATERIALS thermotolerance of preparation improves more obvious, and mechanical property remains unchanged basically, explains that the raising that SEEPS content increases resistance toheat has great role; And the CABLE MATERIALS good flame resistance of preparation, soft more, feel is fine.Because the content of TPU descends, so the oil resistant of material, wear resisting property also have the performance of decline.But still can meet the requirement of CABLE MATERIALS.The cable surface that makes is smooth and be mute light effect, and no fire retardant moves after placement for some time, is suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Embodiment 5:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 15.
The preparation method is following: take by weighing each component according to composition of raw materials; Earlier styrenic elastomerics (SEBS) is added in the stirrer; Spray softening agent (industrial white oil); Stirred 30 minutes, again with TPU, novel phosphor nitrogen combustion inhibitor, silicon-dioxide, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
Testing method is with embodiment 1.
Test result is shown in table 2 embodiment 5; Compare embodiment 2; Present embodiment adopts styrenic elastomerics SEBS and thermoplastic polyurethane elastomer to carry out melt blending; The result shows: the CABLE MATERIALS mechanical property of preparation is high, and good flame resistance can be through UL 1581 vertical combustion VW-1 test.Resistance toheat is high, can reach 105 ℃ of temperature resistant grades.Goods oil resistant, wear-resisting and cable is soft flexible, smooth surface and be mute light effect, place for some time after no fire retardant move, be suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Embodiment 6:
The ratio of the starting material component in the prescription is carried out with reference to embodiment in the table 16.
The preparation method is following: take by weighing each component according to composition of raw materials; Earlier styrenic elastomerics (SEPS) is added in the stirrer; Spray softening agent (industrial white oil); Stirred 30 minutes, again with TPU, novel phosphor nitrogen combustion inhibitor, silicon-dioxide, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
Testing method is with embodiment 1.
Test result is shown in table 2 embodiment 6; Compare embodiment 2; Present embodiment adopts styrenic elastomerics SEPS and thermoplastic polyurethane elastomer to carry out melt blending; The result shows: the CABLE MATERIALS mechanical property of preparation is high, and good flame resistance can be through UL 1581 vertical combustion VW-1 test.Resistance toheat is high, can reach 105 ℃ of temperature resistant grades.Goods oil resistant, wear-resisting and cable is soft flexible, smooth surface and be mute light effect, place for some time after no fire retardant move, be suitable as the production of communication cable, shipboard cable, automobile cable and computer peripheral cable.
Comparative Examples 1:
The ratio of the starting material component in the prescription is carried out with reference to Comparative Examples in the table 11.
The preparation method is following: take by weighing each component according to composition of raw materials, with TPU, novel phosphor nitrogen combustion inhibitor, silicon-dioxide, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
Testing method is with embodiment 1.
Compare embodiment 2, do not add SEEPS in this Comparative Examples, test result is shown in table 2 Comparative Examples 1, and the result shows: if do not add SEEPS, the processing temperature narrow range of TPU CABLE MATERIALS can not be stablized and extrude.The temperature resistant grade of CABLE MATERIALS also has only 80 ℃.And the cable feel of preparation is harder.
Comparative Examples 2:
The ratio of the starting material component in the prescription is carried out with reference to Comparative Examples in the table 12.
The preparation method is following: take by weighing each component according to composition of raw materials; Earlier styrenic elastomerics (SEEPS) is added in the stirrer; Spray softening agent (industrial white oil); Stirred 30 minutes, again with TPU, APP fire retardant, silicon-dioxide, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
Testing method is with embodiment 1.
Compare embodiment 2; Adopt traditional APP fire retardant in this Comparative Examples, test result is shown in table 2 Comparative Examples 2, and the result shows: adopt traditional APP fire retardant poor-performing; 0.8mm the print of thickness only can reach the FV-1 grade, and can not be through UL1581 VW-1 test.Because the easy moisture absorption of APP fire retardant, cause and matrix consistency variation, mechanical property descends to some extent, and meets the water capacity and be prone to separate out, and touches up sticking hand phenomenon man-hour adding.
Comparative Examples 3:
The ratio of the starting material component in the prescription is carried out with reference to Comparative Examples in the table 13.
The preparation method is following: take by weighing each component according to composition of raw materials; Earlier styrenic elastomerics (SEEPS) is added in the stirrer; Spray softening agent (industrial white oil); Stirred 30 minutes, again with TPU, novel phosphor nitrogen combustion inhibitor, siloxanes, antioxidant 1010 and 168 and the PE Masterbatch add in the stirrer and stirred 30 minutes, thorough mixing is even.Mixed raw material is added in the twin screw extruder, and rate of feeding is 80rpm/min, and screw speed is 600rpm/min; The length-to-diameter ratio of screw rod is 25, the processing temperature of twin screw: first section is 180 ℃, and second section is 190 ℃; The 3rd section is 190 ℃, and the 4th section is 200 ℃, and the 5th section is 200 ℃; The 6th section is 200 ℃, obtains halogen-free fire retardation thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
Testing method is with embodiment 1.
Compare embodiment 2; Do not add silicon-dioxide in this Comparative Examples, test result is shown in table 2 Comparative Examples 3, and the result shows: do not add very light of cable surface that matting agent silicon-dioxide makes; Can not meet the requirement of client, and skid during lettering and be easy to wipe mute optical surface.
The proportioning of table 1 embodiment and Comparative Examples each component
Each item performance of table 2 embodiment and Comparative Examples
The halogen-free fire retardation thermoplastic polyurethane elastomer cable material of the present invention's preparation has following performance, tensile strength >=20MPa, and elongation at break >=400%, the cable ignition energy is through the experiment of UL VW-1 vertical combustion.105 ℃ of temperature resistant grades, hardness 70 ~ 88A, density 1.20 ~ 1.30, oil resistant, wear-resisting meets the requirement of non-halogen flame-retardant cable.The present invention especially adds after the styrenic elastomerics; The temperature resistant grade of goods is brought up to 105 ℃ by original 80 ℃, can use with sheath material or the Insulation Material done wear resistance, oil-proofness, the high temperature resistant and fire-retardant communication cable that has higher requirements, automobile cable, shipboard cable and computer peripheral cable.
More than a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material how provided by the present invention and preparation method thereof specify.Embodiment has wherein only explained several kinds of concrete embodiments of the present invention, is not the restriction to patent protection interest field of the present invention.
Claims (10)
1. high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material, it is characterized in that: its raw material by following percentage composition is formed:
2. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1, it is characterized in that: TPUE is the TPUE of polyether-type, durometer level is Shao A 60～90.
3. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1 is characterized in that: the styrenic elastomerics is one or more a mixture of styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-butadiene-styrene block copolymer (SIBS), styrene-ethylene-propylene-styrene segmented copolymer (SEPS), styrene-ethylene-(ethylene-propylene)-styrol copolymer (SEEPS).
4. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1 is characterized in that: the softening agent that the present invention adopts is one or more a mixture of industrial white oil, NO, Yellow Protopet 2A.
5. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1, it is characterized in that: expansion type flame retardant is a halogen-free expansion fire retardant.
6. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1 is characterized in that:, matting agent is silicon-containing compound.
7. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1; It is characterized in that: oxidation inhibitor is with four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) is primary antioxidant, three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168) is an auxiliary antioxidant, and the weight ratio of primary antioxidant and auxiliary antioxidant is 3:1.
8. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1 is characterized in that: lubricant is one or more the mixture in Triple Pressed Stearic Acid, Zinic stearas, the amine hydroxybenzene.
9. a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1 is characterized in that: Masterbatch is one or more a blend of PE Masterbatch, PP Masterbatch.
10. the preparation method of a kind of high flame retardant high heat-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable material according to claim 1; It is characterized in that operational path is: at first each component materials is weighed up by proportioning; The styrenic elastomerics is put into stirrer; Through spray equipment spray softening agent, stirred 15 ~ 30 minutes; With stirring 15 ~ 30 minutes in TPUE, fire retardant, lubricant, matting agent, oxidation inhibitor and the Masterbatch adding stirrer, thorough mixing is even.The raw material that mixes is added in the twin screw extruder; Rate of feeding is 10 ~ 80rpm/min, and screw speed is 100 ~ 600rpm/min, and the length-to-diameter ratio of screw rod is 25 ~ 50; Processing temperature is 160 ~ 200 ℃, obtains the thermoplastic polyurethane elastomer cable material pellet through the water-cooled pelletizing.
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| CN103087505A (en) * | 2012-12-21 | 2013-05-08 | 安徽科聚新材料有限公司 | Thermoplastic polyurethane elastomer material and preparation method thereof |
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| CN103483803A (en) * | 2013-09-22 | 2014-01-01 | 东莞市安拓普塑胶聚合物科技有限公司 | Halogen-free full fogging face polyurethane composition and preparation method thereof |
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| CN103756283A (en) * | 2013-12-31 | 2014-04-30 | 上海至正道化高分子材料有限公司 | Low-smoke halogen-free flame retardant oil-resistance super-soft elastomer cable material and preparation method thereof |
| CN103965540A (en) * | 2014-05-16 | 2014-08-06 | 宝胜科技创新股份有限公司 | Cold-resistant and crack-resistant low-smoke, halogen-free and fire-retardant polyolefin sheath material with thermoplasticity and preparation method thereof |
| CN104140633A (en) * | 2014-08-06 | 2014-11-12 | 南通普力马弹性体技术有限公司 | TPE flame resistant material for coating plastic and preparing method of TPE flame resistant material |
| CN104448191A (en) * | 2014-11-10 | 2015-03-25 | 浙江品诺新材料有限公司 | Abrasion-resistant and ageing-resistant polyurethane guide roller and preparation method thereof |
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