CN103554680A - Preparation method of NTC material based on thermoplastic vulcanizate - Google Patents
Preparation method of NTC material based on thermoplastic vulcanizate Download PDFInfo
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- CN103554680A CN103554680A CN201310476561.4A CN201310476561A CN103554680A CN 103554680 A CN103554680 A CN 103554680A CN 201310476561 A CN201310476561 A CN 201310476561A CN 103554680 A CN103554680 A CN 103554680A
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920006342 thermoplastic vulcanizate Polymers 0.000 title abstract description 6
- 239000005060 rubber Substances 0.000 claims abstract description 77
- 229920001971 elastomer Polymers 0.000 claims abstract description 75
- 238000004073 vulcanization Methods 0.000 claims abstract description 45
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 31
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 29
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 29
- 239000004020 conductor Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000009757 thermoplastic moulding Methods 0.000 claims abstract description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 44
- -1 promotor Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- 230000003712 anti-aging effect Effects 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 230000005669 field effect Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920013649 Paracril Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
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- 238000010074 rubber mixing Methods 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- H—ELECTRICITY
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- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
- H01C7/049—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of organic or organo-metal substances
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Abstract
The invention relates to a preparation method of an NTC material based on a thermoplastic vulcanizate (TPV). The method includes the following steps: (1) thoroughly mixing pure rubber and additives through a mixing process to prepare a rubber compound; (2) uniformly dispersing a conductive material in a thermoplastic resin; (3) adding the rubber compound into a high-temperature mixer, and conducting dynamic vulcanization on the rubber compound and the molten thermoplastic resin dispersed with the conductive material; and (4) conducting thermoplastic molding on the products from dynamic vulcanization. According to the invention, the conductive material is dispersed in the TPV continuous phase, so that in case of temperature increase, expansion of the rubber phase strengthens thermoplastic a conductive network in the resin phase, so as to exhibit NTC effect and obtain a conductive NTC material with stable phase structure and NCT properties. The method is simple, and the material has easily controllable conductive properties, good flexibility, low density and feasibility of bulk preparation.
Description
Technical field
The present invention relates to a kind of NTC(negative temperature coefficient, Negative Temperature Coefficient) preparation method of material, be specifically related to a kind of preparation method of the NTC material based on thermoplastic sulfurized rubber, specifically, relate to a kind of a kind of preparation method with the controlled polymer NTC material of rubber snappiness, conductivity who electro-conductive material is scattered in to the resin external phase of thermoplastic sulfurized rubber and obtains.
Background technology
NTC material refers to temperature rising resistance and is the material that exponential relationship reduces, has the thermistor phenomenon of negative temperature coefficient.Common NTC material is that the metal oxide that has a semiconductor property by manganese, cobalt, nickel and copper etc. is main raw, adopts ceramic technique manufacture and prepares.This class material is when temperature is lower, and the current carrier in oxide material (electronics and hole) number is relative less, and causes the resistance value of material self higher; Along with the rising of temperature, current carrier number increases, and the resistance value of material occurs significantly to reduce.Thermistor prepared by NTC material can be widely used in the occasions such as temperature survey, temperature compensation, surge current suppression.In the NTC material of finding report, exist that density is high, complex forming technology, material without pliable and tough can crimp tendency etc. problem.
Polymer based conducting materials is to take macromolecular material as matrix, by the compound material of preparing of the conducting material with some amount, has the advantages such as high molecular low density, well processed formability, technique are simple, resistivity variable range is large, price is low concurrently.Conducting material comprises that carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder (as silver powder, copper powder, aluminium powder, nickel powder, Stainless Steel Powder) and surface are coated with the ceramic fine bead of metal, the mixture of one or more materials in glass microballon.High molecular based PTC (positive temperature coefficient, Positive Temperature Coefficient) material three ten years have in the past obtained widely and have used, and ptc material is along with the rising of temperature, and resistance changes from small to big, and by conductor, is transformed into isolator; In the preparation process of ptc material, try every possible means always to eliminate or be suppressed at and in temperature-rise period, produce the NTC behavior occurring after PTC behavior.
Up to the present, the preparation of the NTC material based on polymer-based seldom relates to, still being actually applied based on elastomeric NTC material truly not.
Goal of the invention and summary of the invention
The present invention is directed to that current NTC density of material is high, fragility is large, can not be curling, the problem such as complex forming technology, a kind of preparation method of the NTC material based on thermoplastic sulfurized rubber has been proposed, the method is simple, electroconductibility is controlled easily, good moldability, goods are pliable and tough can be curling, and given good batch production feasibility.
The preparation method who the invention provides a kind of NTC material based on thermoplastic sulfurized rubber, comprises following order step:
(1) by calendering process, rubber is mixed with vulcanizing agent, promotor, activator, anti-aging agent, scorch retarder, filler, softening wet goods auxiliary agent, make rubber unvulcanizate;
(2) by thermoplastic resin fusion plastification in high-temperature mixer tool, add electro-conductive material, under shearing force field effect, realize dispersed in thermoplastic resin of electro-conductive material;
(3) rubber unvulcanizate is added to high-temperature mixer, and under temperature field and shearing force field effect, carry out dynamic vulcanization with thermoplastic resin melting and that disperseed electro-conductive material;
(4) after dynamic vulcanization completes, take out dynamic vulcanization product, carry out as required thermoplastic molding.
Wherein, described rubber can be selected one or more, and described rubber is any one or its arbitrary combination in natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, chloroprene rubber, ethylene-propylene rubber(EPR) and chlorinated polyethylene rubber; Mixing facilities is opening rubber mixing machine, Banbury mixer, screw-type extruder or torque rheometer.
Described thermoplastic resin is a kind of in polyethylene, polypropylene, polymeric amide, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer and acrylonitrile-butadiene-styrene terpolymer; Described electro-conductive material is any one or its arbitrary combination in carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder and the surface ceramic fine bead that is coated with metal, glass microballon.
Preferred version: described rubber is ethylene-propylene rubber(EPR); Described thermoplastic resin is a kind of in polyethylene and polypropylene; Described electro-conductive material is a kind of of carbon black and carbon nanotube.
Described high-temperature mixer comprises two roller mills, Banbury mixer, screw-type extruder or torque rheometer; For crystalline thermoplastic plastics, the temperature in high-temperature mixer should be higher than 30～50 ℃ of its fusing points; For amorphous thermoplastics, the temperature in high-temperature mixer should be higher than 50～80 ℃ of its second-order transition temperatures.
The time of described dynamic vulcanization should be controlled as under the temperature condition of rubber unvulcanizate in high-temperature mixer, the sulfurizing time of the rubber unvulcanizate that employing vulcanization curve testing tool is tested.
In high-temperature mixer, the mass ratio of described thermoplastic resin and rubber unvulcanizate is controlled at 1:1～2.5.
Control the add-on of electro-conductive material in thermoplastic resin, at ambient temperature, make the volume specific resistance of its dynamic vulcanization product in semi-conductive region (10
3～10
8Ω cm).
In technique scheme, mixing by rubber, is dispersed in the auxiliary agents such as the crosslinking coagents such as vulcanizing agent, promotor, activator, scorch retarder and reinforcement, filler, tenderizer in rubber; Vulcanization system can adopt sulfur cross-linking system, peroxide systems and phenolic resin vulcanization system.Consumption and reinforcement add-on by vulcanizing agent, promotor in vulcanization system, can regulate and control the cross-linking density of the Vulcanized rubber granule in dynamic vulcanization after product and coefficient of thermal expansion; The in the situation that of rising temperature, for the external phase being formed by thermoplastic resin in thermoplastic sulfurized rubber system, the coefficient of expansion of rubber domain is higher, and caused the rising along with temperature, rubber phase has played squeezing action to the external phase of thermoplastic resin, the conducting particles network structure of thermoplastic resin in mutually strengthened, and the resistivity of system declines, and has then played the regulation and control that realize the electroconductibility of the NTC material based on thermoplastic sulfurized rubber.
For the electro-conductive material that is dispersed in thermoplastic resin matrix, can be that carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder and surface are coated with the ceramic fine bead of metal, the mixture of one or more materials in glass microballon, in order to make the volume specific resistance of thermoplastic sulfurized rubber under room temperature condition in semi-conductive region, add carbon nanotube, carbon fiber of one dimension etc., can significantly reduce thermoplastic sulfurized rubber from isolator, to enter the threshold value of semiconductor regions; On the other hand, there is crystalline thermoplastic resin, as polyethylene, polypropylene, polymeric amide, ethylene-vinyl acetate copolymer etc., repulsive interaction due to the crystal in crystallisation process, make to be scattered in the boundary that electro-conductive material major part in thermoplastic resin is excluded from crystal, promote formation and the strengthening of boundary conductive network, and reduced the threshold value of conduction.
Thermoplastic Vulcanizate adopts dynamic vulcanization process to prepare.Dynamic vulcanization refers in the mixing tank of high temperature and high-shear rubber and resin melting blend, under linking agent effect, realize the original position sulfuration of rubber and be scattered in resin with molecule, forming and take crosslinked in a large number rubber particles this has the stable dispersion system of unique phase structure as disperse phase, a small amount of thermoplastics are external phase.Compared with uncrosslinked or lightly crosslinked Rubber-Plastics Blends, the mechanical property that dynamic vulcanization system tool is significantly improved, this is due to due to the more stable reason of the form of crosslinked rubber particles.
In the preparation of the NTC material based on thermoplastic sulfurized rubber, the too high levels of rubber phase, conductive network in thermoplastic resin external phase has been played to iris action, and reduced thus electroconductibility, improved the resistivity of system, the mass ratio of thermoplastic resin phase and rubber phase is that 1:1～2.5 are more suitable.
Before dynamic vulcanization, first rubber and vulcanizing agent, promotor, activator, anti-aging agent, scorch retarder, filler, softening wet goods auxiliary agent mixes, make rubber unvulcanizate, afterwards rubber unvulcanizate and thermoplastic resin are carried out to dynamic vulcanization, can avoid directly by thermoplastic resin, when rubber and auxiliary agent are mixed into Mobile state sulfuration, vulcanizing agent, promotor, activator, anti-aging agent, scorch retarder, filler, softening wet goods auxiliary agent is to excessive migration and diffusion in resin-phase, and cause the performance controllability of rubber phase to reduce, guaranteed the regulating and controlling of performance of vulcanized rubber in product thermoplastic sulfurized rubber TPV.
The mensuration of NTC performance: use vulcanizing press composite copper foil as electrode on the sample two sides of preparing by dynamic vulcanization, be cut into the small pieces of 10 * 10mm size, be placed in vacuum drying oven Program and heat up, by digital multimeter or resistance test instrument test record data, draw resistance-temperature curve.
The present invention compared with prior art, has positively effect and advance significantly:
(1) the present invention, by electro-conductive material being scattered in to the external phase of thermoplastic sulfurized rubber, makes in the situation that temperature raises, and the expansion of rubber phase is strengthened the conductive network in resin-phase, presents NTC effect;
(2) first electro-conductive material is dispersed in the thermoplastic resin of fusion plastification, promoted the formation of conductive network in thermoplastic resin, also avoided directly by electro-conductive material, thermoplastic resin, rubber unvulcanizate mixing and dynamic vulcanization process, caused electro-conductive material to excessive migration and diffusion in rubber, avoided the destruction of conductive network;
(3) compare with the NTC material based on metal oxide of report, the method is simple, and the conductivity of product is easily controlled, and gives snappiness, the low density that goods are good and prepare in batches feasibility.
Accompanying drawing explanation
Volume specific resistance-thetagram that Fig. 1 is polyethylene/ethylene-propylene rubber(EPR)/carbon black type NTC material of preparing by the inventive method.
Volume specific resistance-thetagram that Fig. 2 is polypropylene/ethylene-propylene rubber(EPR)/carbon nano tube type NTC material of preparing by the inventive method.
Embodiment
Embodiment 1:
A preparation method for the NTC material of thermoplastic sulfurized rubber, comprises following order step:
(1) sizing compound formula: in mass fraction, ethylene-propylene rubber(EPR) 100, sulphur 1, tetramethyl-thiuram disulfide (Vulcanization accelerator TMTD) 1, N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ) 2, zinc oxide 5, stearic acid 1.5,2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD) 2;
(2) in above-mentioned sizing material ratio, on the twin-screw extruder of 60 ℃, by ethylene-propylene rubber(EPR) and the mixing master batch of evenly making of various Synergist S-421 95, lower;
(3) 60 grams of polyvinyl resins are placed on the high temperature twin-screw extruder of 160 ℃ after fusion plastification, add 24.0 grams of N220 type carbon blacks, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 68 grams of ethylene-propylene rubber(EPR) is joined to high temperature twin-screw extruder, the polyvinyl resin mixture of preparing with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization condition is (160 ℃ * t
90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t
90be 9 ' 18 ' ', dynamic vulcanization finishes latter lower;
(5) by dynamic vulcanization sample on vulcanizing press in 160 ℃ of preheating 3min, exhaust 3～5 times, pressurize 8min then, takes out slice after the 8min that colds pressing, sample is prepared in cut-parts.
Embodiment 2:
A preparation method for the NTC material of thermoplastic sulfurized rubber, comprises following order step:
(1) sizing compound formula: in mass fraction, ethylene-propylene rubber(EPR) 100, sulphur 1, tetramethyl-thiuram disulfide (Vulcanization accelerator TMTD) 1, N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ) 2, zinc oxide 5, stearic acid 1.5,2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD) 2;
(2) in above-mentioned sizing material ratio, on the twin-screw extruder of 60 ℃, by ethylene-propylene rubber(EPR) and the mixing master batch of evenly making of various Synergist S-421 95, lower;
(3) 48 grams of polyethylene and ethylene copolymers resins are placed on the high temperature twin-screw extruder of 160 ℃ after fusion plastification, add 4.1 grams of carbon nanotubes, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 81.6 grams of ethylene-propylene rubber(EPR) is joined to high temperature twin-screw extruder, the polyvinyl resin mixture of preparing with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization condition is (160 ℃ * t
90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t
90be 9 ' 18 ' ', dynamic vulcanization finishes latter lower;
(5) by dynamic vulcanization sample on vulcanizing press in 160 ℃ of preheating 3min, exhaust 3～5 times, pressurize 8min then, takes out slice after the 8min that colds pressing, sample is prepared in cut-parts.
Embodiment 3:
A preparation method for the NTC material of thermoplastic sulfurized rubber, comprises following order step:
(1) sizing compound formula: in mass fraction, ethylene-propylene rubber(EPR) 100, sulphur 1, tetramethyl-thiuram disulfide (Vulcanization accelerator TMTD) 0.5, N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ) 2, zinc oxide 5, stearic acid 1.5,2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD) 2;
(2) in above-mentioned sizing material ratio, on the twin-screw extruder of 60 ℃, by ethylene-propylene rubber(EPR) and the mixing master batch of evenly making of various Synergist S-421 95, lower;
(3) 60 grams of polypropylene copolymer resins are placed on the high temperature twin-screw extruder of 170 ℃ after fusion plastification, add 23 grams of N220 type carbon blacks, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 68 grams of ethylene-propylene rubber(EPR) is joined to high temperature twin-screw extruder, the acrylic resin mixture of preparing with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization condition is (170 ℃ * t
90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t
90be 6 ' 58 ' ', dynamic vulcanization finishes latter lower;
(5) by dynamic vulcanization sample on vulcanizing press in 160 ℃ of preheating 3min, exhaust 3～5 times, pressurize 8min then, takes out slice after the 8min that colds pressing, sample is prepared in cut-parts.
Embodiment 4:
A preparation method for the NTC material of thermoplastic sulfurized rubber, comprises following order step:
(1) sizing compound formula: in mass fraction, ethylene-propylene rubber(EPR) 100, sulphur 1, tetramethyl-thiuram disulfide (Vulcanization accelerator TMTD) 0.5, N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ) 2, zinc oxide 5, stearic acid 1.5,2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD) 2;
(2) in above-mentioned sizing material ratio, on the twin-screw extruder of 60 ℃, by ethylene-propylene rubber(EPR) and the mixing master batch of evenly making of various Synergist S-421 95, lower;
(3) 48 grams of polypropylene copolymer resins are placed on the high temperature twin-screw extruder of 170 ℃ after fusion plastification, add 4.2 grams of carbon nanotubes, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 81.6 grams of ethylene-propylene rubber(EPR) is joined to high temperature twin-screw extruder, the acrylic resin mixture of preparing with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization condition is (170 ℃ * t
90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t
90be 6 ' 58 ' ', dynamic vulcanization finishes latter lower;
(5) by dynamic vulcanization sample on vulcanizing press in 160 ℃ of preheating 3min, exhaust 3～5 times, pressurize 8min then, takes out slice after the 8min that colds pressing, sample is prepared in cut-parts.
Other embodiment:
Preparation technology is the same.
Claims (9)
1. a preparation method for the NTC material based on thermoplastic sulfurized rubber, comprises following order step:
(1) by calendering process, rubber is mixed with vulcanizing agent, promotor, activator, anti-aging agent, scorch retarder, filler, softening wet goods auxiliary agent, make rubber unvulcanizate;
(2) by thermoplastic resin fusion plastification in high-temperature mixer tool, add electro-conductive material, under shearing force field effect, realize dispersed in thermoplastic resin of electro-conductive material;
(3) rubber unvulcanizate is added to high-temperature mixer, and under temperature field and shearing force field effect, carry out dynamic vulcanization with thermoplastic resin melting and that disperseed electro-conductive material;
(4) after dynamic vulcanization completes, take out dynamic vulcanization product, carry out as required thermoplastic molding.
2. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, it is characterized in that: described rubber can be selected one or more, described rubber is any one or its arbitrary combination in natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, chloroprene rubber, ethylene-propylene rubber(EPR) and chlorinated polyethylene rubber; Mixing facilities is opening rubber mixing machine, Banbury mixer, screw-type extruder or torque rheometer.
3. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 2, is characterized in that: described rubber is ethylene-propylene rubber(EPR).
4. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, is characterized in that: described thermoplastic resin is a kind of in polyethylene, polypropylene, polymeric amide, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer and acrylonitrile-butadiene-styrene terpolymer; Described electro-conductive material is any one or its arbitrary combination in carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder and the surface ceramic fine bead that is coated with metal, glass microballon.
5. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 4, is characterized in that: described thermoplastic resin is any one in polyethylene, polypropylene; Described electro-conductive material is any one of carbon black and carbon nanotube.
6. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, is characterized in that: described high-temperature mixer comprises two roller mills, Banbury mixer, screw-type extruder or torque rheometer; For crystalline thermoplastic plastics, the temperature in high-temperature mixer should be higher than 30～50 ℃ of its fusing points; For amorphous thermoplastics, the temperature in high-temperature mixer should be higher than 50～80 ℃ of its second-order transition temperatures.
7. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, it is characterized in that: the time of described dynamic vulcanization should be controlled as under the temperature condition of rubber unvulcanizate in high-temperature mixer the sulfurizing time of the rubber unvulcanizate that employing vulcanization curve testing tool is tested.
8. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, is characterized in that: in high-temperature mixer, the mass ratio of described thermoplastic resin and rubber unvulcanizate is controlled at 1:1～2.5.
9. the preparation method of the NTC material based on thermoplastic sulfurized rubber according to claim 1, it is characterized in that: control the add-on of electro-conductive material in thermoplastic resin, at ambient temperature, make the volume specific resistance of its dynamic vulcanization product in semi-conductive region (10
3～10
8Ω cm).
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| CN104497394A (en) * | 2014-12-11 | 2015-04-08 | 郑州大学 | Polymer based temperature-sensitive resistance material with negative temperature coefficient (NTC) effect and preparation method thereof |
| CN106383928A (en) * | 2016-08-30 | 2017-02-08 | 西华大学 | Method for constructing high-temperature plastic flow densification constitutive models of powder sintering materials |
| CN112341681A (en) * | 2020-11-26 | 2021-02-09 | 中国石油大学(北京) | Rubber-plastic blending modified hydrogenated nitrile rubber and preparation method and application thereof |
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2013
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104497394A (en) * | 2014-12-11 | 2015-04-08 | 郑州大学 | Polymer based temperature-sensitive resistance material with negative temperature coefficient (NTC) effect and preparation method thereof |
| CN104497394B (en) * | 2014-12-11 | 2016-07-06 | 郑州大学 | Polymer-matrix thermo-sensitive resistor material with negative temperature coefficient effect and preparation method thereof |
| CN106383928A (en) * | 2016-08-30 | 2017-02-08 | 西华大学 | Method for constructing high-temperature plastic flow densification constitutive models of powder sintering materials |
| CN106383928B (en) * | 2016-08-30 | 2019-09-20 | 西华大学 | A kind of sintered powder material high-temp plastic rheology densification constitutive model construction method |
| CN112341681A (en) * | 2020-11-26 | 2021-02-09 | 中国石油大学(北京) | Rubber-plastic blending modified hydrogenated nitrile rubber and preparation method and application thereof |
| CN112341681B (en) * | 2020-11-26 | 2022-02-11 | 中国石油大学(北京) | Rubber-plastic blending modified hydrogenated nitrile rubber and preparation method and application thereof |
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