CN103554680B - A kind of preparation method of the NTC material based on thermoplastic sulfurized rubber - Google Patents

A kind of preparation method of the NTC material based on thermoplastic sulfurized rubber Download PDF

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CN103554680B
CN103554680B CN201310476561.4A CN201310476561A CN103554680B CN 103554680 B CN103554680 B CN 103554680B CN 201310476561 A CN201310476561 A CN 201310476561A CN 103554680 B CN103554680 B CN 103554680B
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rubber
thermoplastic resin
electro
dynamic vulcanization
conductive material
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CN103554680A (en
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王兆波
李帅
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Qingdao University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions 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
    • C08L23/28Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06Copolymers with styrene
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-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
    • H01C7/04Non-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
    • H01C7/049Non-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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/04Thermoplastic elastomer

Abstract

The present invention relates to a kind of preparation method based on the NTC material of thermoplastic sulfurized rubber (TPV), comprise following order step: gum, by calendering process, mixes with auxiliary agent by (1), makes rubber unvulcanizate; (2) electro-conductive material is dispersed in thermoplastic resin; (3) rubber unvulcanizate is added high-temperature mixer, and with melting and disperseed the thermoplastic resin of electro-conductive material to carry out dynamic vulcanization; (4) thermoplastic molding is carried out to dynamic vulcanization product.The present invention is by being scattered in the external phase of TPV by electro-conductive material, make at an elevated temperature, conductive network during the expansion of rubber phase makes thermoplastic resin is mutually strengthened, and presents NTC effect, obtains a kind of conduction NCT material with stable Phase stracture and NTC performance.The method is simple, and the conductivity of material easily controls, and has good snappiness, low density and feasibility of batch preparation.

Description

A kind of preparation method of the NTC material based on thermoplastic sulfurized rubber
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 electro-conductive material is scattered in thermoplastic sulfurized rubber resin external phase and a kind of preparation method with the controlled polymer NTC material of rubber snappiness, conductivity obtained.
Background technology
NTC material refers to the exponentially relation reduction of temperature rising resistance, the material with the thermistor phenomenon of negative temperature coefficient.Common NTC material is the metal oxide having a semiconductor property by manganese, cobalt, nickel and copper etc. is main raw, adopts the manufacture technics of pottery and prepares.This kind of material is when temperature is lower, and current carrier (electronics and the hole) number in oxide material 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, also exist that density is high, complex forming technology, material be without problems such as pliable and tough rollable property.
Polymer based conducting materials take macromolecular material as matrix, the material prepared by the conducting material compound with some amount, the advantage such as have high molecular low density, well processed formability concurrently, technique is simple, resistivity variable range is large, price is low.Conducting material comprises the mixture 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 one or more materials in the ceramic fine bead of metal, glass microballon.High molecular based PTC (positive temperature coefficient, Positive Temperature Coefficient) material three ten years in the past obtain and use widely, and ptc material is along with the rising of temperature, and resistance changes from small to big, and is transformed into isolator by conductor; In the preparation process of ptc material, the NTC behavior occurred after trying every possible means to eliminate or suppress to produce PTC behavior in temperature-rise period always.
Up to the present, the preparation based on polymer-based NTC material seldom relates to, still not being actually applied based on elastomeric NTC material truly.
Goal of the invention and summary of the invention
The present invention is directed to that current NTC material density is high, fragility greatly, the problem such as not rollable, complex forming technology, propose a kind of preparation method of the NTC material based on thermoplastic sulfurized rubber, the method is simple, electroconductibility controls easily, good moldability, goods are pliable and tough rollable, and impart good batch production feasibility.
The invention provides a kind of preparation method of the NTC material based on thermoplastic sulfurized rubber, comprise 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, makes 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 high-temperature mixer, and with melting and disperseed the thermoplastic resin of electro-conductive material to carry out dynamic vulcanization under temperature field and shearing force field effect;
(4), after dynamic vulcanization completes, take out dynamic vulcanization product, carry out thermoplastic molding as required.
Wherein, described rubber can select 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 the one in polyethylene, polypropylene, polymeric amide, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer and acrylonitrile-butadiene-styrene terpolymer; Any one or its arbitrary combination in the ceramic fine bead that described electro-conductive material is carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder and surface are coated with metal, glass microballon.
Preferred version: described rubber is ethylene-propylene rubber(EPR); Described thermoplastic resin is the one in polyethylene and polypropylene; Described electro-conductive material is the one of carbon black and carbon nanotube.
Described high-temperature mixer comprises two roller mill, Banbury mixer, screw-type extruder or torque rheometer; For crystalline thermoplastic plastics, the temperature in high-temperature mixer should higher than its fusing point 30 ~ 50 DEG C; For amorphous thermoplastics, the temperature in high-temperature mixer should higher than its second-order transition temperature 50 ~ 80 DEG C.
Time of described dynamic vulcanization should control as under the temperature condition of rubber unvulcanizate in high-temperature mixer, the sulfurizing time of the rubber unvulcanizate adopting vulcanization curve testing tool to test.
In high-temperature mixer, the mass ratio of described thermoplastic resin and rubber unvulcanizate controls in 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 be in the region (10 of semi-conductor 3~ 10 8Ω cm).
In technique scheme, mixing by rubber, is dispersed in rubber by auxiliary agents such as the crosslinking coagents such as vulcanizing agent, promotor, activator, scorch retarder and reinforcement, filler, tenderizers; Vulcanization system can adopt sulfur cross-linking system, peroxide systems and phenolic resin vulcanization system.By consumption and the reinforcement add-on of 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; When raised temperature, relative in thermoplastic sulfurized rubber system for the external phase that thermoplastic resin is formed, the coefficient of expansion of rubber domain is higher, and the rising that result in along with temperature, the external phase of rubber phase to thermoplastic resin serves squeezing action, conducting particles network structure in making thermoplastic resin is mutually strengthened, and the resistivity of system declines, and then serves the regulation and control realized based on the electroconductibility of the NTC material of thermoplastic sulfurized rubber.
For the electro-conductive material being dispersed in thermoplastic resin matrix, it can be the mixture that carbon black, graphite, expanded graphite, carbon nanotube, carbon fiber, metal-powder and surface are coated with one or more materials in the ceramic fine bead of metal, glass microballon, the region of semi-conductor is in order to make the volume specific resistance of thermoplastic sulfurized rubber under room temperature condition, add the carbon nanotube of one dimension, carbon fiber etc., significantly can reduce thermoplastic sulfurized rubber enters semiconductor regions threshold value from isolator; On the other hand, there is crystalline thermoplastic resin, as polyethylene, polypropylene, polymeric amide, ethylene-vinyl acetate copolymer etc., due to the repulsive interaction of the crystal in crystallisation process, the electro-conductive material major part be scattered in thermoplastic resin is made to be excluded from the boundary of crystal, facilitate formation and the strengthening of boundary conductive network, and reduce the threshold value of conduction.
Thermoplastic Vulcanizate adopts dynamic vulcanization process to prepare.Dynamic vulcanization refer in the mixing tank of high temperature and high-shear by rubber and resin melting blended, under linking agent effect, realize the In-situ sulphiding of rubber and be scattered in resin with molecule, formed with rubber particles crosslinked be in a large number disperse phase, a small amount of thermoplastics is external phase this has the stable dispersion system of unique Phase stracture.More uncrosslinked or lightly crosslinked Rubber-Plastics Blends, the mechanical property that dynamic vulcanization system tool is significantly improved, this is caused by the more stable reason of the form of crosslinked rubber particles.
In preparation based on the NTC material of thermoplastic sulfurized rubber, the too high levels of rubber phase, iris action is served by the conductive network in thermoplastic resin external phase, and thus reduce electroconductibility, improve 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 dynamic vulcanization, can avoid thermoplastic resin directly, 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 the excessive migration in resin-phase and diffusion, and cause the performance controllability of rubber phase to reduce, ensure that the controllable of the performance of vulcanized rubber in product thermoplastic sulfurized rubber TPV.
The mensuration of NTC performance: using the sample two sides vulcanizing press composite copper foil prepared by dynamic vulcanization as electrode, be cut into the small pieces of 10 × 10mm size, be placed in vacuum drying oven Program to 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 is by being scattered in the external phase of thermoplastic sulfurized rubber by electro-conductive material, makes at an elevated temperature, and the expansion of rubber phase makes the conductive network in resin-phase be strengthened, and presents NTC effect;
(2) first electro-conductive material is dispersed in the thermoplastic resin of fusion plastification, facilitate the formation of conductive network in thermoplastic resin, it also avoid directly by electro-conductive material, thermoplastic resin, rubber unvulcanizate mixing and dynamic vulcanization process, cause electro-conductive material to the excessive migration in rubber and diffusion, avoid the destruction of conductive network;
(3) with report based on metal oxide NTC material compared with, the method is simple, and the conductivity of product easily controls, and gives the good snappiness of goods, low density and feasibility of batch preparation.
Accompanying drawing explanation
Fig. 1 is the volume specific resistance-thetagram of the polyethylene/ethylene-propylene rubber(EPR)/carbon black type NTC material prepared by the inventive method.
Fig. 2 is the volume specific resistance-thetagram of the polypropylene/ethylene-propylene rubber(EPR)/carbon nano tube type NTC material prepared by the inventive method.
Embodiment
Embodiment 1:
Based on a preparation method for the NTC material of thermoplastic sulfurized rubber, comprise 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) by above-mentioned size ratio, on the twin-screw extruder of 60 DEG C, by ethylene-propylene rubber(EPR) and various Synergist S-421 95 is mixing evenly makes master batch, bottom sheet;
(3) on the high temperature twin-screw extruder 60 grams of polyvinyl resins being placed in 160 DEG C after fusion plastification, add N220 type carbon black 24.0 grams, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 68 grams of ethylene-propylene rubber(EPR) is joined high temperature twin-screw extruder, the polyvinyl resin mixture prepared with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization conditions is (160 DEG C × t 90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t 90be 9 ' 18 ' ', dynamic vulcanization terminates rear bottom sheet;
(5) by dynamic vulcanization sample on vulcanizing press in 160 DEG C of preheating 3min, be vented 3 ~ 5 times, then pressurize 8min, take out slice after 8min of colding pressing, sample is prepared in cut-parts.
Embodiment 2:
Based on a preparation method for the NTC material of thermoplastic sulfurized rubber, comprise 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) by above-mentioned size ratio, on the twin-screw extruder of 60 DEG C, by ethylene-propylene rubber(EPR) and various Synergist S-421 95 is mixing evenly makes master batch, bottom sheet;
(3) on the high temperature twin-screw extruder 48 grams of polyethylene copolymer resin being placed in 160 DEG C after fusion plastification, add carbon nanotube 4.1 grams, 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 high temperature twin-screw extruder, the polyvinyl resin mixture prepared with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization conditions is (160 DEG C × t 90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t 90be 9 ' 18 ' ', dynamic vulcanization terminates rear bottom sheet;
(5) by dynamic vulcanization sample on vulcanizing press in 160 DEG C of preheating 3min, be vented 3 ~ 5 times, then pressurize 8min, take out slice after 8min of colding pressing, sample is prepared in cut-parts.
Embodiment 3:
Based on a preparation method for the NTC material of thermoplastic sulfurized rubber, comprise 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) by above-mentioned size ratio, on the twin-screw extruder of 60 DEG C, by ethylene-propylene rubber(EPR) and various Synergist S-421 95 is mixing evenly makes master batch, bottom sheet;
(3) on the high temperature twin-screw extruder 60 grams of polypropylene copolymer resin being placed in 170 DEG C after fusion plastification, add N220 type carbon black 23 grams, regulation and control cylinder gap is 1 millimeter, mixing 3 minutes;
(4) rubber unvulcanizate of 68 grams of ethylene-propylene rubber(EPR) is joined high temperature twin-screw extruder, the acrylic resin mixture prepared with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization conditions is (170 DEG C × t 90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t 90be 6 ' 58 ' ', dynamic vulcanization terminates rear bottom sheet;
(5) by dynamic vulcanization sample on vulcanizing press in 160 DEG C of preheating 3min, be vented 3 ~ 5 times, then pressurize 8min, take out slice after 8min of colding pressing, sample is prepared in cut-parts.
Embodiment 4:
Based on a preparation method for the NTC material of thermoplastic sulfurized rubber, comprise 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) by above-mentioned size ratio, on the twin-screw extruder of 60 DEG C, by ethylene-propylene rubber(EPR) and various Synergist S-421 95 is mixing evenly makes master batch, bottom sheet;
(3) on the high temperature twin-screw extruder 48 grams of polypropylene copolymer resin being placed in 170 DEG C after fusion plastification, add carbon nanotube 4.2 grams, 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 high temperature twin-screw extruder, the acrylic resin mixture prepared with the step (3) of melting carries out dynamic vulcanization, and dynamic vulcanization conditions is (170 DEG C × t 90), for the ethylene-propylene rubber(EPR) rubber unvulcanizate in present embodiment, its t 90be 6 ' 58 ' ', dynamic vulcanization terminates rear bottom sheet;
(5) by dynamic vulcanization sample on vulcanizing press in 160 DEG C of preheating 3min, be vented 3 ~ 5 times, then pressurize 8min, take out slice after 8min of colding pressing, sample is prepared in cut-parts.
Other embodiment:
Preparation technology is the same.

Claims (1)

1., based on a preparation method for the NTC material of thermoplastic sulfurized rubber, comprise following order step:
(1) by calendering process, rubber is mixed with vulcanizing agent, promotor, activator, anti-aging agent, scorch retarder, filler, softening oil, makes rubber unvulcanizate;
(2) by thermoplastic resin fusion plastification in high-temperature mixer, add electro-conductive material, under shearing force field effect, realize dispersed in thermoplastic resin of electro-conductive material;
(3) rubber unvulcanizate is added high-temperature mixer, and with melting and disperseed the thermoplastic resin of electro-conductive material to carry out dynamic vulcanization under temperature field and shearing force field effect;
(4), after dynamic vulcanization completes, take out dynamic vulcanization product, carry out thermoplastic molding as required;
Wherein, in high-temperature mixer, the mass ratio of described thermoplastic resin and rubber unvulcanizate controls in 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 be in the region of semi-conductor.
CN201310476561.4A 2013-10-12 2013-10-12 A kind of preparation method of the NTC material based on thermoplastic sulfurized rubber Expired - Fee Related CN103554680B (en)

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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
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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