CN102408606B - Flame-retardant PTC (positive temperature coefficient) polymer electroconductive material and preparation method thereof - Google Patents

Flame-retardant PTC (positive temperature coefficient) polymer electroconductive material and preparation method thereof Download PDF

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Publication number
CN102408606B
CN102408606B CN2011102587100A CN201110258710A CN102408606B CN 102408606 B CN102408606 B CN 102408606B CN 2011102587100 A CN2011102587100 A CN 2011102587100A CN 201110258710 A CN201110258710 A CN 201110258710A CN 102408606 B CN102408606 B CN 102408606B
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ethylene
weight parts
vinyl
flame retardant
conducting material
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CN102408606A (en
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计晓荣
宋义虎
强弱
强虎贲
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XI'AN GAIWO THERMAL ENERGY TECHNOLOGY Co.,Ltd.
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XI'AN GWARM THERMAL TECHNOLOGY Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention relates to a flame-retardant PTC (positive temperature coefficient) polymer electroconductive material, which is prepared from the following raw materials in parts by weight: polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-octylene copolymer, carbon black, carbon fiber, dicumyl peroxide, vinyl silane coupling agent, dodecyl benzene sulfonic acid, nano aluminum hydroxide, ammonium polyphosphate, pentaerythritol and organic montmorillonite. The flame-retardant PTC polymer electroconductive material has excellent flame retardancy and electric conductivity, stable performance and long life, and is free of additives harmful to human bodies and environment. The preparation method of the flame-retardant PTC polymer electroconductive material comprises weighing raw materials, primarily granulating and secondly granulating. The preparation method has simple process flow and wide raw material sources, and is easy to realize.

Description

Flame retardant type PTC macromolecule conducting material and preparation method thereof
Technical field
The invention belongs to the thermo electric material preparing technical field, be specifically related to a kind ofly be used to make from limitting flame retardant type PTC macromolecule conducting material of warm Electric radiant Heating Film and preparation method thereof.
Background technology
Planar electrothermal heating product mainly is made up of semi-conductor heating element, current-carrying bar, insulating material.The main product of low-temp radiating electrothermal membrane is to be processed by the electrically conductive ink current-carrying bar, the silver powder coating bus-bar that are clipped in the parallel connection between insulation polyester (PET) film, and Electric radiant Heating Film is communicated with power supply through lead, and electric energy is converted into heat energy.U.S.'s Calorique Electric radiant Heating Film contains two-layer insulation polyester film, and the middle line of ink marker is an electrically conductive ink, thick about 0.2mm～0.3mm.(publication number is CN1255037 to one Chinese patent application numbers 99111331.4; Be 2000.05.31 in open day) a kind of " low-temp radiating electrothermal membrane " disclosed; (publication number is CN1874619 to one Chinese patent application numbers 200610010213.8; Be 2006.12.06 in open day) a kind of " electric heating ground film " disclosed, one Chinese patent application number 92106555.8 (publication number is CN1080109, and open day is 1993.12.29) disclose " a kind of complex electrocaloric film "; One Chinese patent application number 91112670.8 (publication number is CN1074074, and open day is 1993.07.07) disclose " a kind of novel electric heating film ".Low-temp radiating electrothermal membrane adopts silk screen print method that electrically conductive ink is transferred on the stock through half tone more.(publication number is CN1440219 to one Chinese patent application number 03110936.5; Open day is 2003.09.03) " a kind of Electric radiant Heating Film method of manufacture " disclosed; Adopt the intaglio printing technology that electrically conductive ink is printed on the bus that formation is arranged in parallel on the PET basement membrane; The bus two ends are connected and compound bus-bar by printing ink, cover another basement membrane on the Electric radiant Heating Film.(publication number is CN101148939 to one Chinese patent application numbers 200710036025.7; Open day is 2008.03.26) " a kind of electric heating floor " disclosed; Adopt silk screen printing technology printing coatings electric membranous layer on substrate; The Electric radiant Heating Film upper strata is provided with insulation layer, can under 36V～220V voltage, long-term safety use.(publication number is CN102083246A to one Chinese patent application numbers 201010562200.8; Open day is 2011.06.01) " a kind of far-infrared electrothermal film " disclosed; Conductive silver paste bar, the orthogonal thereto arrangement of conductive carbon paste bar; Place in the middle of the two-layer insulation film, electric conversion rate reaches 98%, and heating temp is no more than 80 ℃.One Chinese patent application 03146405.X (publication number is CN1571588, and open day is 2005.01.26) discloses " unidirectional heat radiating electrothermal membrane ", adopts the specular reflection functional membrane to make heat energy only to single side radiation.One Chinese patent application 200910010841.X (publication number is CN101534582, and open day is 2005.01.26) discloses " far-infrared electrothermal film blanket ", contains printing ink (carbon element) Electric radiant Heating Film, leather layer, resist, thermal insulation layer, waterproof layer, transmitter etc.(publication number is CN102128467A to one Chinese patent application numbers 201110062060.2; Be 2011.07.20 in open day), 201110060629.1 (publication number is CN102131317A; Open day be 2011.07.20) " electric heating ground film heating plant ", " anticreep and anti-electromagnetic radiation electric heating ground film and preparation method thereof " disclosed respectively; Even printing-ink bus on the polyester film, both sides, outside are laid conductive aluminum foil band, PE big envelope, PVC successively and are protected big envelope.
Other technology of making low-temp radiating electrothermal membrane comprises spraying method, gluing method, pickling process, stamped method etc.(publication number is CN1413064 to one Chinese patent application number 01128297.5; Being 2003.04.23 in open day) (publication number is CN101541110 to " a kind of method of manufacture of nano electroheating film and the heating panel of processing with nano electroheating film ", one Chinese patent application numbers 200910106860.2; Open day is 2009.09.23) " making method of nano electroheating mould material and nano electroheating device ", all conductive coating spray forms Electric radiant Heating Film on substrate.(publication number is CN101431837 to one Chinese patent application numbers 200710047983.4; Being 2009.05.13 in open day) (publication number is CN1060325 to " a kind of far-infrared flexible electric heating material and preparation method thereof and use ", one Chinese patent application numbers 90106391.6; Open day is 1992.04.15) " energy-saving electrothermal membrane snow melter and method for making and purposes "; All electrically conducting coating is coated with and attaches basement membrane on (polyester film, adhesive plaster etc.), install parallelly connected electrode, supply lead after the drying additional.(publication number is CN1258186 to one Chinese patent application numbers 99117279.5; Being 2000.06.28 in open day) (publication number is CN101346017 for " a kind of method of manufacture of heating element of flexible electrothermal membrane ", one Chinese patent application 200810118187.X; Open day is 2009.01.14) " polymer electric heating membrane and application thereof "; Then, again electrically conducting coating evenly is coated in substrate surface and forms Electric radiant Heating Film, fixed insulation resist on it at the preset electrode of flexible macromolecule membrane surface.One Chinese patent application number 89107751.0 (publication number is CN1051059, and open day is 1991.05.01) disclose " a kind of transparent semiconductor electric heating film ", with SbCl 3, CdCl 2Doping SnO 2Semiconductor layer is a sticker with butyl carbitol acetate, polyisobutene, cyclohexanone, is primary solvent with the absolute ethyl alcohol, adopts dip-coating and stoving process on substrate material, to form semiconductor film membranous type Electric radiant Heating Film.(publication number is CN101568201 to one Chinese patent application numbers 200810036591.2; Open day is 2009.10.28) " double-guide heating element " disclosed; Its electric heating piece comprises that insulated substrate (polyester film or refreshing wood glue plank), two are stamped in the lip-deep low temperature irradiation Electric radiant Heating Film of insulated substrate (electrically conductive ink, carbon wafer or carbon fibre); Two Electric radiant Heating Film stagger at interval, electrode is in alignment with each other, and can eliminate hertzian wave effectively.
The carbon element facial heating sheet is another kind of main flow low-temp radiating electrothermal membrane.The heating main body of the farsighted hard Heating ground heating system of Korea S HALLA Co., Ltd. is the embedded planar heat producing body of nano carbon and non-woven fabrics, and totally 11 layers of total thickness 0.7mm have the intelligent temperature control function, and self temperature is no more than 60 ℃.(publication number is CN102123529A to one Chinese patent application numbers 201110059086.1; Being 2011.07.13 in open day) Electric radiant Heating Film that disclosed of " a kind of novel carbon fiber complex electrocaloric film and preparation method thereof ", one Chinese patent application number 00121583.3 (publication number is CN1338885, open day be 2002.03.06) " low-temp radiating electrothermal carbon fibre membrane and preparation method thereof " contains the netted braid(ed)ply of conductive carbon fibre, two ends metal electrode, is insulated the heat-conducting plastic film.(publication number is CN101237723 to one Chinese patent application numbers 200710006388.6; Open day be 2008.08.06) " Electric radiant Heating Film reaches with its prepared Electric radiant Heating Film and electric heating device with constituent " disclosed; Electrically conducting coating is coated on the network-like filamentary material (like carbon fiber paper, metal fibre paper, metallized fibre paper), and thermofixation obtains the Electric radiant Heating Film of the female resistance value in 10～1200 Europe.(publication number is CN1606384 to one Chinese patent application numbers 200310107851.8; Be 2005.04.13 in open day) " folding change tetrafluoroethylene Electric radiant Heating Film and preparation method thereof " disclosed; To conduct electricity the mixing of teflon resin dispersion liquid, granulation, drying, add extrusion aid, be shaped to round strip with the pushing machine; Be compressed to fibrous film with rolling press, except that being sintered to soft tough fibrous Electric radiant Heating Film behind the extrusion aid.
Has resistance positive temperature coefficient (positive temperature coefficient; PTC) the inorganic or organic materials of effect can be used for making from temperature control type intelligence Electric radiant Heating Film; The PTC function can prevent that local anomaly is overheated, and control current is effectively controlled current consumption with variation of temperature automatically.The permanent PTC of the thermo electric material Science and Technology Ltd. Electric radiant Heating Film far away of commercially produced product such as Korea S DYMSCO (prosperous greatly) PTC infrared electric heating film, Shandong is translucent polyester film and electrically conductive ink low temperature adhesion and process.The fertile heating system intelligently of Zhejiang Huayuan Electric Heat Co., Ltd.'s match comprises the filled polyethylene that 1.2mm is thick, 34cm is wide (PE) type PTC semiconductor element, utilizes the thermistor characteristic to realize the active temperature control of Electric radiant Heating Film.(publication number is CN1056393 to one Chinese patent application numbers 90102752.9; Be 1991.11.20 in open day) " the composite conductive polymer electric heating body with flexible and thermostatic characteristics " disclosed; Employing contains the compound curable macromolecular material of 15-60% conductive filler and makes resistive layer; The two sides covers insulation layer, and heating element surface or inside add casing ply.(publication number is CN1663002 to one Chinese patent application number 03814070.5; Be 2005.08.31 in open day), 200510134568.3 (publication number is CN1790557; Be 2006.06.21 in open day), 200910003413.4 (publication number is CN101521963; Open day is 2009.09.02) " flexible PCT heating element and method of manufacture thereof " disclosed, substrate surface is provided with concavo-convex foamed resin or elastomeric material, adopts printing technology on flexible parent metal, to form PTC resistance, electrode.(publication number is CN1791308 to one Chinese patent application numbers 200510045421.7; Open day is 2006.06.21) " heating film manufacturing method and relevant heating element thereof " disclosed; Utilize the water-soluble metallized resistive ink above the insulation layer or utilize auxiliary mould; After gold-plated or vacuum plating becomes electrode line, do not form the top of electrode layer and become specified shape perhaps not form the top coating film of electrode line with the PTC ink printing.
Summary of the invention
The purpose of this invention is to provide a kind of flame retardant type PTC macromolecule conducting material, had excellent flame and electroconductibility, stable performance, long service life does not contain human body, the deleterious additive of environment.
Another object of the present invention provides the preparation method of this flame retardant type PTC macromolecule conducting material.
The technical scheme that the present invention adopted is; A kind of flame retardant type PTC macromolecule conducting material; It is characterized in that feed composition is made up of following composition: polyvinyl resin 100 weight parts, ethylene-vinyl acetate copolymer 5～55 weight parts, ethylene-octene copolymer 5～25 weight parts, carbon black 15～55 weight parts, thomel 5～25 weight parts, Di Cumyl Peroxide 99 0.001～0.010 weight part, vinyl silicane coupling agent 0.1～2.0 weight part, Witco 1298 Soft Acid 0.1～2.0 weight part, nano-aluminum hydroxide 5～20 weight parts, ammonium polyphosphate 5～20 weight parts, tetramethylolmethane 5～20 weight parts and organo montmorillonite 1～10 weight part.
Wherein, polyvinyl resin is high-density polyethylene resin, ldpe resin, linear low density polyethylene or medium-density polyethylene resin.It is 10%～28% vinyl acetate between to for plastic ester units that ethylene-vinyl acetate copolymer contains weight percentage.It is 9%～28% octene unit that ethylene-octene copolymer contains weight percentage.Vinyl silicane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane tri-butyl peroxy, vinyl silane triisopropoxide, silane coupling A-172 or 3-methacryloxypropyl trimethoxy silane.
Another technical scheme that the present invention adopted is that the preparation method of flame retardant type PTC macromolecule conducting material is characterized in that, may further comprise the steps:
Step 1, take by weighing following raw material and form:
Polyvinyl resin 100 weight parts; Ethylene-vinyl acetate copolymer 5～55 weight parts; Ethylene-octene copolymer 5～25 weight parts; Carbon black 15～55 weight parts; Thomel 5～25 weight parts; Di Cumyl Peroxide 99 0.001～0.010 weight part; Vinyl silicane coupling agent 0.1～2.0 weight part; Witco 1298 Soft Acid 0.1～2.0 weight part; Nano-aluminum hydroxide 5～20 weight parts; Ammonium polyphosphate 5～20 weight parts; Tetramethylolmethane 5～20 weight parts; And organo montmorillonite 1～10 weight part;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, carbon black, vinyl silicane coupling agent, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane and organo montmorillonite that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 2min～5min adopts forcing machine extruding pelletization under 130 ℃～220 ℃ temperature with the mixture that obtains;
Step 3, granulation for the second time:
After polyvinyl resin, thomel and the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 130 ℃～220 ℃ temperature, promptly get.
Wherein, polyvinyl resin is high-density polyethylene resin, ldpe resin, linear low density polyethylene or medium-density polyethylene resin.It is 10%～28% vinyl acetate between to for plastic ester units that ethylene-vinyl acetate copolymer contains weight percentage.It is 9%～28% octene unit that ethylene-octene copolymer contains weight percentage.Vinyl silicane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane tri-butyl peroxy, vinyl silane triisopropoxide, silane coupling A-172 or 3-methacryloxypropyl trimethoxy silane.
Flame retardant type PTC macromolecule conducting material of the present invention is mainly used in and produces from limitting warm Electric radiant Heating Film, and its beneficial effect is:
1, uses nano-aluminum hydroxide, ammonium polyphosphate, the composite flame-retardant agent of tetramethylolmethane composition and ethylene-vinyl acetate copolymer, the ethylene-octene copolymer properties-correcting agent of ratio of the present invention of ratio of the present invention; It can not only improve the flame retardant properties of flame retardant type PTC macromolecule conducting material of the present invention; The present invention is being made into when limitting warm Electric radiant Heating Film goods, has excellent flexibility and mar-resistance.
2, adopt organo montmorillonite and nano-aluminum hydroxide regulation and control ethylenic copolymer (comprising ethylene-vinyl acetate copolymer, ethylene-octene copolymer) viscosity; Conducting particles (being carbon black, thomel) is dispersed in the ethylenic copolymer; The restriction conducting particles spreads in ethylenic copolymer at flame retardant type PTC macromolecule conducting material extruding pelletization of the present invention and follow-up the limit in the warm Electric radiant Heating Film production process certainly; Can reduce percolation threshold, conductivity of the present invention is provided.
3, vinyl silicane coupling agent both can promote the dispersion of conducting particles carbon black, thomel; Can make polyvinyl resin, ethylene-vinyl acetate copolymer, ethylene-octene copolymer form crosslinking structure again; And conductive component is fixed in the cross-linked polymer network; Thereby the gathering of restriction conducting particles in limitting warm Electric radiant Heating Film use certainly improves use properties stability of the present invention.
4, the raw material composition is drawn materials extensively, and does not contain human body, the deleterious additive of environment.
Preparing method's of the present invention beneficial effect is that technical process is simple, draws materials extensively, is easy to realize.
Embodiment
Flame retardant type PTC macromolecule conducting material of the present invention, feed composition is made up of following composition: polyvinyl resin 100 weight parts, ethylene-vinyl acetate copolymer 5～55 weight parts, ethylene-octene copolymer 5～25 weight parts, carbon black 15～55 weight parts, thomel 5～25 weight parts, Di Cumyl Peroxide 99 0.001～0.010 weight part, vinyl silicane coupling agent 0.1～2.0 weight part, Witco 1298 Soft Acid 0.1～2.0 weight part, nano-aluminum hydroxide 5～20 weight parts, ammonium polyphosphate 5～20 weight parts, tetramethylolmethane 5～20 weight parts and organo montmorillonite 1～10 weight part.
Wherein, polyvinyl resin is high-density polyethylene resin, ldpe resin, linear low density polyethylene or medium-density polyethylene resin.It is 10%～28% vinyl acetate between to for plastic ester units that ethylene-vinyl acetate copolymer contains weight percentage.It is 9%～28% octene unit that ethylene-octene copolymer contains weight percentage.Vinyl silicane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane tri-butyl peroxy, vinyl silane triisopropoxide, silane coupling A-172 or 3-methacryloxypropyl trimethoxy silane.
The present invention does not limit the method for modifying and the properties-correcting agent of organo montmorillonite, preferably uses the palmityl trimethyl ammonium chloride modified montmorillonoid.The present invention does not limit the model and the size of thomel, and preferred thomel is that long 0.5mm～4mm and diameter Distribution are the chopped carbon fiber of 1 μ m～10 μ m.Carbon black uses acetylene black and Ketjen black usually.
The preparation method of flame retardant type PTC macromolecule conducting material of the present invention may further comprise the steps:
Step 1, take by weighing following raw material and form:
Polyvinyl resin 100 weight parts; Ethylene-vinyl acetate copolymer 5～55 weight parts; Ethylene-octene copolymer 5～25 weight parts; Carbon black 15～55 weight parts; Thomel 5～25 weight parts; Di Cumyl Peroxide 99 0.001～0.010 weight part; Vinyl silicane coupling agent 0.1～2.0 weight part; Witco 1298 Soft Acid 0.1～2.0 weight part; Nano-aluminum hydroxide 5～20 weight parts; Ammonium polyphosphate 5～20 weight parts; Tetramethylolmethane 5～20 weight parts; And organo montmorillonite 1～10 weight part;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, carbon black, vinyl silicane coupling agent, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane and organo montmorillonite that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 2min～5min adopts forcing machine extruding pelletization under 130 ℃～220 ℃ temperature with the mixture that obtains;
Step 3, granulation for the second time:
After polyvinyl resin, thomel and the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 130 ℃～220 ℃ temperature again, promptly get.
The dispersion of carbon black in ethylenic copolymer (comprising ethylene-vinyl acetate copolymer, ethylene-octene copolymer) is one of key of preparation method of the present invention.Preparing method of the present invention carries out the extruding pelletization first time earlier, and raw materials such as carbon black are scattered in ethylene-vinyl acetate copolymer, the ethylene-octene copolymer, promotes sooty to disperse with unitary polarity of vinyl acetate and vinyl silicane coupling agent.Again because, the ethylene-vinyl acetate copolymer viscosity is lower, carbon black is reunited in extrusion process easily.As nano-aluminum hydroxide, the ammonium polyphosphate of flame retardant compositions, and, can improve the viscosity of ethylene-vinyl acetate copolymer, ethylene-octene copolymer, help the dispersion of carbon black in the extruding pelletization process as the organo montmorillonite of viscosity-controlling agent.
The distribution in flame retardant type PTC macromolecule conducting material of the present invention of the degree that is separated of ethylenic copolymer and polyvinyl resin and carbon black be preparation method of the present invention key two.If with the disposable mixing of all feed composition, extruding pelletization, carbon black are distributed in polyvinyl resin according to qualifications, are unfavorable for the electric thermal power that reduces the percolation threshold of electro-conductive material and improve its Electric radiant Heating Film of processing.Adopt preparation method of the present invention; The first time ethylenic copolymer compsn pellet that granulation obtains and polyvinyl resin, thomel, Di Cumyl Peroxide 99 mixture the second time extruding pelletization process in, the increasing glutinous effect and can limit the degree of being separated of nano-aluminum hydroxide, ammonium polyphosphate and organo montmorillonite.Simultaneously, this time the shearing action of extrusion impels carbon black to polyethylene/vinyl-vinyl acetate copolymer, polyethylene/vinyl-octene copolymer interfacial migration and the enrichment at the interface, helps reducing percolation threshold.In addition, thomel was introduced in the extruding pelletization process in the second time, and thomel can be across Vilaterm phase, ethylene-vinyl acetate copolymer, ethylene-octene copolymer phase, and connected the carbon black conductive passage, played the effect that reduces percolation threshold.And percolation threshold is low more, and resistivity is more little, and the conductivity of electro-conductive material is just good more.
Flame retardant type PTC macromolecule conducting material conductivity of the present invention stability and limit certainly the control of the electric heating function stability of warm Electric radiant Heating Film be preparation method of the present invention key three.Among the preparation method of the present invention, vinyl silicane coupling agent, Di Cumyl Peroxide 99 add in twice extruding pelletization process respectively.In first time extruding pelletization process, vinyl silicane coupling agent has the carbon black of promotion and nano-aluminum hydroxide, ammonium polyphosphate, the effect of organo montmorillonite dispersive.Extrude for the second time and to cause in the process; Vilaterm and ethylenic copolymer produce radical under Di Cumyl Peroxide 99 causes; Realize the vinyl silicane coupling agent graft modification, and particles such as finely disseminated carbon black and nano-aluminum hydroxide, ammonium polyphosphate, organo montmorillonite are fixed on the macromolecular chain.Therefore, after steam was crosslinked, particles such as carbon black and nano-aluminum hydroxide, ammonium polyphosphate, organo montmorillonite were fixed on the conductive network, can improve electric heating property stability based on the temperature of the limit certainly Electric radiant Heating Film of flame retardant type PTC macromolecule conducting material of the present invention.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1
Step 1, take by weighing following raw material and form:
100kg ldpe resin, 5kg vinyl acetate unit weight percentage ratio are 9% ethylene-vinyl acetate copolymer, and 25kg octene unit weight percentage ratio is 9% ethylene-octene copolymer; 15kg acetylene black, 25kg length distribution are that 0.5mm～4mm and diameter Distribution are the T300 chopped carbon fiber of 1 μ m～10 μ m, the 1g Di Cumyl Peroxide 99; 0.1kg vinyltrimethoxy silane; 0.1kg Witco 1298 Soft Acid, 5kg nano-aluminum hydroxide, 20kg ammonium polyphosphate; 5kg tetramethylolmethane, and 1kg palmityl trimethyl ammonium chloride modified montmorillonoid;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, acetylene black, vinyltrimethoxy silane, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane and palmityl trimethyl ammonium chloride modified montmorillonoid that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 2min adopts forcing machine extruding pelletization under 130 ℃ of temperature with the mixture that obtains;
Step 3, granulation for the second time:
After ldpe resin, T300 chopped carbon fiber and the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 130 ℃ of temperature again, promptly get flame retardant type PTC macromolecule conducting material.
The flame retardant type PTC macromolecule conducting material that makes is positioned in the mould; Adopt press at 160 ℃ of temperatures system 10min; Processing diameter is that 25mm and thickness are the disk shape sample of 2mm, presses copper net electrode on two circular sections up and down at this disk shape sample while hot.The volt ohm-milliammeter test resistance is adopted in the cooling back, and getting 7 these sample resistivity test result MVs is 2300 ± 180 Ω cm.The bar shaped sample of the long 100mm of preparation, wide 6.5mm, thick 2mm under similarity condition, the test oxygen index is 28.
Embodiment 2
Step 1, take by weighing following raw material and form:
100kg high-density polyethylene resin, 55kg vinyl acetate unit weight percentage ratio are 28% ethylene-vinyl acetate copolymer, and 5kg octene unit weight percentage ratio is 28% ethylene-octene copolymer; 55kg Ketjen black, 5kg length distribution are that 0.5mm～4mm and diameter Distribution are the T300 chopped carbon fiber of 1 μ m～10 μ m, the 10g Di Cumyl Peroxide 99; The 2kg vinyltriethoxysilane; The 2kg Witco 1298 Soft Acid, 20kg nano-aluminum hydroxide, 5kg ammonium polyphosphate; 20kg tetramethylolmethane, and 10kg palmityl trimethyl ammonium chloride modified montmorillonoid;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, Ketjen black, vinyltriethoxysilane, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane, palmityl trimethyl ammonium chloride modified montmorillonoid that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 5min; The mixture that obtains is adopted forcing machine extruding pelletization under 220 ℃ of temperature
Step 3, granulation for the second time:
After high-density polyethylene resin, T300 chopped carbon fiber, the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 220 ℃ of temperature again, promptly get flame retardant type PTC macromolecule conducting material.
The flame retardant type PTC macromolecule conducting material that makes is positioned in the mould; Adopt press at 160 ℃ of temperatures system 10min; Processing diameter is that 25mm and thickness are the disk shape sample of 2mm, presses copper net electrode on two circular sections up and down at this disk shape sample while hot.The volt ohm-milliammeter test resistance is adopted in the cooling back, and getting 7 these sample resistivity test result MVs is 2300 ± 180 Ω cm.The bar shaped sample of the long 100mm of preparation, wide 6.5mm, thick 2mm under similarity condition, the test oxygen index is 31.
Embodiment 3
Step 1, take by weighing following raw material and form:
100kg linear low density polyethylene, 30kg vinyl acetate unit weight percentage ratio are 18% ethylene-vinyl acetate copolymer, and 15kg octene unit weight percentage ratio is 18% ethylene-octene copolymer; 35kg Ketjen black, 15kg length distribution are that 0.5mm～4mm and diameter Distribution are the T300 chopped carbon fiber of 1 μ m～10 μ m, the 5g Di Cumyl Peroxide 99; The 1kg vinyl silane tri-butyl peroxy; The 1kg Witco 1298 Soft Acid, 12kg nano-aluminum hydroxide, 12kg ammonium polyphosphate; 12kg tetramethylolmethane, and 5kg palmityl trimethyl ammonium chloride modified montmorillonoid;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, Ketjen black, vinyl silane tri-butyl peroxy, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane, palmityl trimethyl ammonium chloride modified montmorillonoid that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 3min adopts forcing machine extruding pelletization under 180 ℃ of temperature with the mixture that obtains;
Step 3, granulation for the second time:
After linear low density polyethylene, T300 chopped carbon fiber, the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 180 ℃ of temperature again, promptly get flame retardant type PTC macromolecule conducting material.
The flame retardant type PTC macromolecule conducting material that makes is positioned in the mould; Adopt press at 160 ℃ of temperatures system 10min; Processing diameter is that 25mm and thickness are the disk shape sample of 2mm, presses copper net electrode on two circular sections up and down at this disk shape sample while hot.The volt ohm-milliammeter test resistance is adopted in the cooling back, and getting 7 these sample resistivity test result MVs is 1840 ± 30 Ω cm.The batten sample of the long 100mm of preparation, wide 6.5mm, thick 2mm under similarity condition, the test oxygen index is 27.
Embodiment 4
Adopt the high-density polyethylene resin in the medium-density polyethylene resin alternate embodiment 2, other adopts the vinyltriethoxysilane in the vinyl silane triisopropoxide alternate embodiment 2, and all the other step conditions are with embodiment 2.
Embodiment 5
Adopt the high-density polyethylene resin in the medium-density polyethylene resin alternate embodiment 2, other adopts the vinyltriethoxysilane in silane coupling A-172 alternate embodiment 2, and all the other step conditions are with embodiment 2.
Embodiment 6
Adopt the high-density polyethylene resin in the medium-density polyethylene resin alternate embodiment 2, other adopts the vinyltriethoxysilane in the 3-methacryloxypropyl trimethoxy silane alternate embodiment 2, and all the other step conditions are with embodiment 2.

Claims (10)

1. flame retardant type PTC macromolecule conducting material; It is characterized in that feed composition is made up of following composition: polyvinyl resin 100 weight parts, ethylene-vinyl acetate copolymer 5～55 weight parts, ethylene-octene copolymer 5～25 weight parts, carbon black 15～55 weight parts, thomel 5～25 weight parts, Di Cumyl Peroxide 99 0.001～0.010 weight part, vinyl silicane coupling agent 0.1～2.0 weight part, Witco 1298 Soft Acid 0.1～2.0 weight part, nano-aluminum hydroxide 5～20 weight parts, ammonium polyphosphate 5～20 weight parts, tetramethylolmethane 5～20 weight parts and organo montmorillonite 1～10 weight part.
2. according to the said flame retardant type PTC of claim 1 macromolecule conducting material, it is characterized in that said polyvinyl resin is high-density polyethylene resin, ldpe resin, linear low density polyethylene or medium-density polyethylene resin.
3. according to the said flame retardant type PTC of claim 1 macromolecule conducting material, it is characterized in that it is 10%～28% vinyl acetate between to for plastic ester units that said ethylene-vinyl acetate copolymer contains weight percentage.
4. according to the said flame retardant type PTC of claim 1 macromolecule conducting material, it is characterized in that it is 9%～28% octene unit that said ethylene-octene copolymer contains weight percentage.
5. according to the said flame retardant type PTC of claim 1 macromolecule conducting material; It is characterized in that said vinyl silicane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane tri-butyl peroxy, vinyl silane triisopropoxide, silane coupling A-172 or 3-methacryloxypropyl trimethoxy silane.
6. the preparation method of a flame retardant type PTC macromolecule conducting material is characterized in that, may further comprise the steps:
Step 1, take by weighing following raw material and form:
Polyvinyl resin 100 weight parts; Ethylene-vinyl acetate copolymer 5～55 weight parts; Ethylene-octene copolymer 5～25 weight parts; Carbon black 15～55 weight parts; Thomel 5～25 weight parts; Di Cumyl Peroxide 99 0.001～0.010 weight part; Vinyl silicane coupling agent 0.1～2.0 weight part; Witco 1298 Soft Acid 0.1～2.0 weight part; Nano-aluminum hydroxide 5～20 weight parts; Ammonium polyphosphate 5～20 weight parts; Tetramethylolmethane 5～20 weight parts; And organo montmorillonite 1～10 weight part;
Step 2, granulation for the first time:
Ethylene-vinyl acetate copolymer, ethylene-octene copolymer, carbon black, vinyl silicane coupling agent, Witco 1298 Soft Acid, nano-aluminum hydroxide, ammonium polyphosphate, tetramethylolmethane and organo montmorillonite that step 1 is taken by weighing add in the high-speed mixer; Mixed at high speed 2min～5min adopts forcing machine extruding pelletization under 130 ℃～220 ℃ temperature with the mixture that obtains;
Step 3, granulation for the second time:
After polyvinyl resin, thomel and the Di Cumyl Peroxide 99 that pellet that step 2 is obtained and step 1 take by weighing mixes, adopt forcing machine extruding pelletization under 130 ℃～220 ℃ temperature, promptly get.
7. according to the preparation method of the said flame retardant type PTC of claim 6 macromolecule conducting material, it is characterized in that said polyvinyl resin is high-density polyethylene resin, ldpe resin, linear low density polyethylene or medium-density polyethylene resin.
8. according to the preparation method of the said flame retardant type PTC of claim 6 macromolecule conducting material, it is characterized in that it is 10%～28% vinyl acetate between to for plastic ester units that said ethylene-vinyl acetate copolymer contains weight percentage.
9. according to the preparation method of the said flame retardant type PTC of claim 6 macromolecule conducting material, it is characterized in that it is 9%～28% octene unit that said ethylene-octene copolymer contains weight percentage.
10. according to the preparation method of the said flame retardant type PTC of claim 6 macromolecule conducting material; It is characterized in that said vinyl silicane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl silane tri-butyl peroxy, vinyl silane triisopropoxide, silane coupling A-172 or 3-methacryloxypropyl trimethoxy silane.
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