CN110183783A - A kind of thermoplastic elastomer (TPE) and preparation method thereof for taking into account mechanical property and electric conductivity - Google Patents
A kind of thermoplastic elastomer (TPE) and preparation method thereof for taking into account mechanical property and electric conductivity Download PDFInfo
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- C08J3/20—Compounding polymers with additives, e.g. colouring
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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
- C08L23/02—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
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a kind of thermoplastic elastomer (TPE)s and preparation method thereof for taking into account mechanical property and electric conductivity, belong to thermoplastic elastic material technical field, component are as follows: non-polar rubber, polyolefin resin, conducting medium, maleic anhydride are grafted non-polar rubber, maleic anhydride stem grafting polyolefin resin, polar rubber, crosslinking agent, assistant crosslinking agent, white oil, inorganic filler, antioxidant, lubricant, light stabilizer, coupling agent, release agent.This method are as follows: conducting medium is subjected to surface active pretreatment first；Then with polyolefin resin melt blending；It is again basis material with non-polar rubber, polar rubber, maleic anhydride grafting non-polar rubber, maleic anhydride grafting non-polar resin, conducting medium, is crosslinked and is made after introducing types of functionality auxiliary agent.The present invention takes into account mechanical property, and the high easy processing of mobility under the premise of guaranteeing has the advantages that good antistatic, and weatherability and resistance to ag(e)ing are good, are of great significance to the application field for widening thermoplastic elastomer (TPE).
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer (TPE)s and preparation method thereof for taking into account mechanical property and electric conductivity, belong to thermoplastic elastic
Body field of material technology.
Background technique
It between rubber and plastics is a kind of composite structured high performance material that thermoplastic elastomer (TPE), which is physical property, it
Not only with the elasticity of rubber, but also the workability with plastics.One new " raw material of industry system " has been constituted, has been by person
" third generation rubber ".It is known as TPE (Thermoplastic by elastomer prepared by substrate of styrene block copolymers
Elastome), can be machined with general thermoplastic plastics shaping, high production efficiency, processing performance is superior, can without vulcanization
Cost is reduced to be recycled, soft-touch has preferable weatherability, fatigue resistance and temperature tolerance.With ethylene propylene diene rubber
Elastomer for substrate preparation is known as TPV (Thermoplastic Vulcanization), because Technology of Dynamic Vulcanized makes system
Interior continuous phase and dispersed phase form three-dimensional network shape island structure and gain the name.Its own possesses the physics of thermoset rubber at normal temperature
Performance and functional character possess the high fluidity and reprocessabilty of thermoplastic at high temperature, so that product possesses molding
The features such as simple processing, material is Ke Xunhuanliyong, cost performance is high.It is both widely used to auto industry at present, builds
The fields such as material, electronic apparatus, health care and consumer appliance.Such as application No. is public in the Chinese patent of CN 101696279
Open the component and proportion of composition described in a kind of method for preparing thermoplastic elastomer through dynamic vulcanization are as follows: synthetic rubber 10~
70%, synthetic resin 30~40%, softening agent 10~30, inorganic filler 5~20%, crosslinking agent 3~10%, promotor 0.6~6
Part.The elastomer that the invention this method produces has the characteristics that high fluidity, high resiliency, soft, and in technique also
Have many advantages, such as that equipment is applicable extensively, preparation process is simple, process window mouth width.
Since thermoplastic elastomer (TPE) sheet is easy between article as insulating material when it serves as coating product, cargo conveying
Electrostatic phenomenon is generated, Precision Machining occasion is jeopardized for height and easily causes harm, therefore inevitable is become for material static elimination, and
The method antistatic modified to thermoplastic elastomer (TPE) is to add conducting medium in the material.Conductive for elastomeric material at present
Mechanism is mainly three classes, it may be assumed that seepage theory, tunnel-effect are theoretical and field emission is theoretical.Seepage theory, also known as conductive path reason
By the theory thinks that conducting medium contacts with each other to form continuous conductive path and then generate conduction in nonconducting elastomer
Network and make materials conductive；Tunnel-effect theory thinks the electronics transition between conducting medium being activated by material thermal vibration
Caused by tunnel current formed conduction；Field emission theory thinks that under high voltages interfacial effect makes conducting particles violent
It moves and mutually hits, generate heavy current between electronics and generate transmitting electric field, be further driven to electronics and break through energy barrier to be formed
Electric current makes elastomer conductive.Three kinds of theories exist simultaneously in elastomeric material, work of being active respectively under different occasions
With, and the improvement for material antistatic at present, it is based primarily upon seepage theory and is carried out.
Antistatic elastomer is mainly used in the industries such as electronic device package, industry security protection, medical analysis.Such as applying
Number to disclose the group of composition described in the TPV elastomeric material that a kind of electrical property improves in the Chinese patent of CN 102051000
Divide and match are as follows: polypropylene 15~60%, ethylene propylene diene rubber 20~60%, polymer bulking agents 0.5~10%, filler 0.1
~40%, rubber filling oil 1~60%, modifying agent 0.5~10%, crosslinking agent 0.5~10%, cross-linking aid 0.1~10%, anti-
Oxygen agent 0.01~2%, processing aid 0.01~10%.The TPV elastomeric material that the electrical property of invention preparation improves, lower
It can reach preferable antistatic effect in the case where additive amount, expand TPV answering in anti-static material and conductive material field
With.
Based on seepage theory, the conducting particles in system must reach a certain concentration and just be able to achieve monolithic conductive, i.e., conductive critical
Threshold value, for different conducting particles under same elastomer, threshold limit value is had nothing in common with each other, it is however generally that, high conductivity
Its threshold limit value of conducting particles is lower, and vice versa.Therefore, for general antistatic elastomer, mainly lead elastomer
The mode of electricity is that electric conductivity is improved by two ways, and one kind is introduced a small amount of high conductivity as described in CN 102051000
Carbon nanotube realize that drawback is that carbon nanotube price itself is higher, and it is simple introduce carbon nanotube and not to it
Good control dispersion is carried out, there is the influence to product itself mechanical property and its processability；Another kind introduces a large amount of
Conductive black, drawback be as do not carried out good working process, then needed for additive amount of the conductive black in whole system
It is excessive, the mechanical property and product mobility of product certainly will be reduced.Therefore, product electrical property, mechanical property, processing performance are realized
High performance-price ratio take into account, become the certainty for preparing antistatic elastomer.
Summary of the invention
To solve the above problems, the invention discloses a kind of thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity and
Preparation method, antistatic material obtained have not only taken into account good electric conductivity and mechanical property, also have good processing
Property and resistance to ag(e)ing, and cheap preparation is easy, and has very big market latent in electronic device package, industry security protection
Power.Its specific technical solution is as follows:
A kind of thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity, in parts by weight, including following components:
30-40 parts of non-polar rubber,
20-30 parts of polyolefin resin,
20-30 parts of conducting medium,
Maleic anhydride is grafted non-polar rubber 0-10 parts,
0-10 parts of maleic anhydride stem grafting polyolefin resin,
0-10 parts of polar rubber,
0.08-0.8 parts of crosslinking agent,
0.6-6 parts of assistant crosslinking agent,
0-40 parts of white oil,
0-20 parts of inorganic filler,
0-0.5 parts of antioxidant,
0-5 parts of dispersing agent,
0-0.5 parts of light stabilizer,
0-5 parts of coupling agent,
0-1 parts of release agent.
Further, the crosslinking agent is tert-butylperoxy isopropyl carbonate, cumyl peroxide or octyl phenolic
One of or any number of combination, the inorganic filler be one of calcium carbonate, talcum powder or white carbon black or any number of combination,
The assistant crosslinking agent is diphenyl-methane maleimide, triisopropyl isocyanates, allyl methacrylate, dimethyl allene
One of sour glycol ester or stannous chloride or any number of combination.
Further, the non-polar rubber is one or both of polyolefin elastomer or styrene block copolymers group
It closes, the maleic anhydride grafting non-polar rubber is the polyolefin elastomer or modified by maleic acid anhydride graft of modified by maleic acid anhydride graft
The combination of one or both of styrene block copolymers, the polar rubber is in nitrile rubber or neoprene
One or two combination.
Further, the polyolefin resin is one in polyethylene, polypropylene or polyethylene and polyacrylic mixture
Kind or any number of combination, the maleic anhydride stem grafting polyolefin resin are polyethylene, the maleic acid of modified by maleic acid anhydride graft
The polypropylene of acid anhydride graft modification and one of the polyethylene of modified by maleic acid anhydride graft and polypropylene or any number of combination.
Further, the polyolefin elastomer is the ethylene propylene diene rubber of Mooney viscosity 20-100, and the styrenic block is total
The styrene-butadiene-styrene or hydrogenated styrene-butadiene that polymers is number-average molecular weight 50000-300000 are embedding
Section copolymer, the polar rubber are the nitrile rubber or neoprene of Mooney viscosity 20-100.
Further, the conducting medium be partial size be 10-20nm, the thermal cracking carbon black of meta-alkalescence；
The conducting medium is DBP absorption value 300-500ml/g, iodine absorption value 800-1000Mg/g, specific surface area 750-
1100m2/ kg, resistivity≤0.5% Ω .m.
Further, the coupling agent is titanate coupling agent, silane coupling agent or titanate coupling agent and silane coupling agent
One of or any number of combination.
Further, when non-polar rubber is polyolefin elastomer, comprising the following steps:
A), conducting medium is added in coupling agent solution and will be infiltrated, adjust pH value to being in alkalescent, heating water bath stirring, dry
To activation conducting medium；
B), ratio according to claim 1 by polyolefin resin and conducting medium after mixing, dispersing agent is added, through molten
After melting mixing facilities melt blending, conductive agglomerate is obtained；
C), by the resulting conductive agglomerate of step B), polyolefin elastomer, polar rubber, modified by maleic acid anhydride graft polyolefin elastomer,
Maleic acid change grafted polyolefinic resin, conducting medium, inorganic filler, antioxidant, dispersing agent, light stabilizer be uniformly mixed
Afterwards, through melting mixing equipment mixing granulation, intermediate product is both obtained；
D), the intermediate product, white oil, crosslinking agent, assistant crosslinking agent, dispersant is uniform, in melting mixing equipment into
After Mobile state vulcanization, antistatic thermoplastic elastomer (TPE) is made.
Further, when synthetic rubber is styrene block copolymers, comprising the following steps:
A), conducting medium is added in coupling agent solution and will be infiltrated, adjust pH value to being in alkalescent, heating water bath stirring, dry
To activation conducting medium；
B), in proportion by polyolefin resin and conducting medium after mixing, be added dispersing agent, through melting mixing equipment melt altogether
After mixed, conductive agglomerate is obtained；
C), by the resulting conductive agglomerate of step B), styrene block copolymers, polar rubber, modified by maleic acid anhydride graft horse
The styrene block copolymers of maleic anhydride grafted modification, maleic acid change grafted polyolefinic resin, conducting medium, inorganic fill out
Material, white oil, antioxidant, dispersant are uniform, and after carrying out dynamic vulcanization in melting mixing equipment, antistatic thermoplasticity is made
Elastomer.
Further, the melting mixing equipment is double screw extruder, and process conditions are 160~220 DEG C of temperature, revolving speed 200
~320rpm.Above-mentioned antistatic thermoplastic elastic material is molded thickness 3mm's using vertical injection molding machine under the conditions of 180 DEG C
Print prepares tensile bars using universal sampling machine, the stretching for measuring material is strong using the volume resistance of resistance instrument measurement sample
The processing flowability of degree and elongation at break, material passes through the melt flows under the conditions of 230 DEG C of measuring temperature, load 5/10kg
Index (MFR) characterizes.
The working principle of the invention is:
In order to realize good electric conductivity, it is necessary to which concern influences five factors of elastomer volume resistivity, it may be assumed that (1) elastomer
Self-resistance rate and polarity, the resistivity of (2) filler grain, the resistivity between (3) filler grain, (4) in galvanic circle
In number of particles, (5) conductive path quantity.Therefore, itself elastomer and conduction with preferable polarity and low resistivity
Property excellent filler can prepare and preferably lead antistatic elastomer.It is further known that from elastomer, for synthetic rubber
Speech improves product electric conductivity based on nonpolar polyolefin elastomer and styrene block copolymers is selected, in elastomer used
Portion's viscosity and crystallization possibility should not be higher, influence conducting particles dispersion, and polar rubber is added by modified grafting and increases pole
Property reduce self-resistance rate；From filler angle, product electric conductivity is improved, filler grain resistivity most importantly used is wanted
Low, filler grain can have in elastomer preferably to be dispersed and ensures to be capable of forming more conductive paths between particle.
In order to realize good mechanical property, self assembly behavior can be used and processed, that is, conducting medium surface is allowed to coat one layer of work
Property substance, it is compatible between avoiding carbon black autohemagglutination and promoting macromolecule, and utilize macromolecule viscositys different in elastomer, flowing
Property, the physical properties such as surface potential energy difference, inducing conductive black selectively in certain phases and distributes alternately, and reduces charcoal
The formation of black invalid conductive path realizes preferable electric conductivity using less conductive black to reach, and ensures mechanical property.
The present invention is first by activating hydrocarbon black powder, by wrapping amphiphilic active group chain on surface, on the one hand
Prevent carbon black autohemagglutination from ensuring there is good dispersibility in system, and active group chain possesses longer living chain and can more help
The formation of conductive path between particle, another aspect active group can reduce the surface potential energy between macromolecule, guarantee carbon black
It can be more effectively compatible with macromolecule.Then it will be carried out between a certain proportion of carbon black and good fluidity polyolefin resin pre-
First self assembly mixing, guarantees preferably to be dispersed in the small island structure of formation in polyolefin resin, guarantees particle in polyolefin
More conductive path is capable of forming in resin.Then by increasing product in non-polar rubber inner part graft modification polar rubber
Polarity, while remaining carbon black is added and carries out mechanical blending, dynamic vulcanization is carried out using plyability crosslinking agent later, guarantees synthesis
Rubber forms good crosslinking in smelting equipment so that rubber particles partial size is smaller, formed greater number of synthetic rubber with
The island phase gap interface formed between polyolefin resin, conductive black can be deposited between phase interface, using crosslinking net
There is gap to form conductive path, while being also filled with reinforcement of the gap realization to elastomer.Realization reaches cheap conduction
Carbon black guarantees taking into account to the comprehensive performance of thermoplastic elastomer (TPE) mechanical property, electrical property and product processability.
The beneficial effects of the present invention are:
The thermoplastic elastomer (TPE) provided by the present invention for taking into account mechanical property and electric conductivity, it is multiple using synthetic rubber/polyolefin resin
Zoarium system is substrate, and adds high structural and high-specific surface area conducting medium, by adjusting synthetic rubber, polyolefin resin
With the ratio of conducting medium, and suitable white oil and the control system degree of cross linking are selected, finally prepares simple process, easy processing,
Take into account the antistatic material of electrical property and mechanical property.The compound system is a kind of thermoplasticity cross-linked network structure, is being based on rubber
In the island structure of glue phase and resin phase, conducting medium is more likely formed conductive path using existing interface phase network structure, because
This medium good dispersion, resistance to ag(e)ing is good, has preferable mechanical strength and has both stronger conductive stability.Therefore, in electronics
The similar fields such as device package, industry security protection, medical analysis are a kind of antistatic materials of great application prospect.
Detailed description of the invention
Fig. 1 is that non-polar rubber shows for the micro- enlarged structure of ethylene propylene diene rubber (EPDM), polyolefin resin polypropylene (PP)
Meaning,
Fig. 2 is the micro- enlarged diagram for activating carbon black.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated.It should be understood that following specific embodiments are merely to illustrate this
It invents rather than limits the scope of the invention.
Embodiment 1
Originally the process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1% coupling agent, be put into ethanol solution and be stirred, and it is weak for adjusting PH
Alkalinity makes its hydrolysis, then weighs 20% conductive black, and the conductive black DBP absorption value is 170-185ml/g, iodine absorbs
Value is 360Mg/g, partial size 9-17nm, is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, and obtains pretreatment powder
Afterwards, it weighs 10% conductive black and 25% random polypropylene is added in high-speed mixer, the polypropylene melt flow rate
It is 65 ± 10.Then 2% dispersing agent is added, stirring is processed in double screw extruder after mediating and is granulated, twin-screw extrusion
The temperature of machine heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200
DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 1；
B), 30% ethylene propylene diene rubber is added in conductive agglomerate 1 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-norborneol
Alkene.Then 10% and the identical conductive black of step a) is added.Then be added, 0.2% antioxidant, stir one minute, finally plus
Enter 1% dispersing agent, processes and be granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone
Are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from
Feed opening is to head), revolving speed 260rpm obtains intermediate a1；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate, wherein crosslinking agent is isopropyl peroxide carbonic acid
The tert-butyl ester；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double spiral shells
It processes and is granulated in bar extruder, in granulation process, 20% white oil, double screw extruder heating zone are added by liquid spout
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
Antistatic thermoplastic elastomer (TPE) TPV b1 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 8.4MPa, elongation at break 520%, MFR are 19.8g/10min (5kg).
Embodiment 2
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1% coupling agent, be put into ethanol solution and be stirred, and it is weak for adjusting PH
Alkalinity makes its hydrolysis, then weighs 21% conductive black, and the conductive black DBP absorption value is 170-185ml/g, iodine absorbs
Value is 360Mg/g, partial size 9-17nm, is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, and obtains pretreatment powder
Afterwards, it weighs 7% conductive black and 30% random polypropylene is added in high-speed mixer, the polypropylene melt flow rate is
30±5.Then 1% stabilizer, 0.2% antioxidant is added, stirs one minute, is eventually adding 2% dispersing agent, after mediating one minute
It processes and is granulated in double screw extruder, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170
DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed
300rpm obtains conductive agglomerate 2；
B), 35% ethylene propylene diene rubber is added in conductive agglomerate 2 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 70, ethylene contents 70%, Third monomer content 5%, and Third monomer is ethylidene-norbornene.
Then 7% and the identical conductive black of step a) is added.Then 0.2% stabilizer is added, 0.1% antioxidant stirs one minute,
It is eventually adding 0.4% dispersing agent, processes and is granulated in double screw extruder after mediating one minute, double screw extruder heating zone
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
(sequentially for from feed opening to head), revolving speed 260rpm obtain intermediate a2 (1)；
C), addition 7% and the identical conductive black of step a) are continuously added in intermediate a1.Then 0.1% stabilizer is added,
0.2% dispersing agent is processed in double screw extruder after mediating one minute and is granulated, the temperature setting of double screw extruder heating zone
Are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from
Feed opening is to head), revolving speed 260rpm obtains intermediate a2 (2)；
D), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate, wherein crosslinking agent is isopropyl peroxide carbonic acid
The tert-butyl ester；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double spiral shells
It processes and is granulated in bar extruder, in granulation process, 8% white oil, double screw extruder heating zone are added by liquid spout
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
Antistatic thermoplastic elastomer (TPE) TPV b2 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 12.2MPa, elongation at break 538%, MFR are 6.4g/10min (10kg).
2 main sides of embodiment focus on carbon black and are added in three times, promote carbon black to be further dispersed in thermoplastic elastomer component, add
Compatibility between strong each component selects the lower random polypropylene of melt index and adds more multi-component three compared to embodiment 1
First EP rubbers so that tensile strength and elongation at break further increase, but is also sacrificed on the basis of volume resistivity is close
Portioned product mobility.
Embodiment 3
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1% coupling agent, be put into ethanol solution and be stirred, and it is weak for adjusting PH
Alkalinity makes its hydrolysis, then weighs 20% conductive black, and the conductive black DBP absorption value is 170-185ml/g, iodine absorbs
Value is 360Mg/g, partial size 9-17nm, is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, and obtains pretreatment powder
Afterwards, it weighs 10% conductive black and 25% isotactic polypropylene is added in high-speed mixer, wherein the polypropylene melt flow
Rate is 2 ± 1, isotactic index >=96%；Then 2% dispersing agent is added, stirring is processed in double screw extruder after mediating and made
Grain, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C,
200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 3；
B), 30% ethylene propylene diene rubber is added in conductive agglomerate 1 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-norborneol
Alkene.Then 10% and the identical conductive black of step a) is added.Then be added, 0.2% antioxidant, stir one minute, finally plus
Enter 1% dispersing agent, processes and be granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone
Are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from
Feed opening is to head), revolving speed 260rpm obtains intermediate a3；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate, wherein crosslinking agent is isopropyl peroxide carbonic acid
The tert-butyl ester；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double spiral shells
It processes and is granulated in bar extruder, in granulation process, 20% white oil, double screw extruder heating zone are added by liquid spout
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
Antistatic thermoplastic elastomer (TPE) TPV b3 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
108Ω .cm, tensile strength 11.5MPa, elongation at break 606%, MFR are 1.8g/10min (10kg).
3 main sides of embodiment focus in the selection to polyethylene and are replaced by low-flow isotactic knot by high fluidity random polypropylene
Crystalline substance polypropylene hinders infiltration of the carbon black in polypropylene, it is proper to make due to polyacrylic crystallinity compared to embodiment 1
Conductive path in system reduces, therefore, although the related mechanical strength of system rises, cause volume resistivity it is obvious under
Drop.
Embodiment 4
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 45% ethylene propylene diene rubber and be added in high-speed mixer, the ethylene propylene diene rubber
Mooney viscosity be 65,70% Third monomer content 4.2% of ethylene contents, and Third monomer be ethylidene-norbornene.So
20% isotactic polypropylene and 30% conductive black are once added afterwards, wherein the polypropylene melt flow rate is 4 ± 2, etc.
Advise index >=96%；Conductive black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm.So
After 1% stabilizer, 0.5% antioxidant is added, add 0.2% coupling agent, stir one minute, be eventually adding 2.5% lubricant,
It processes and is granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), revolving speed 300rpm obtains intermediate a4；
B), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a4, wherein crosslinking agent is isopropyl peroxide carbon
Tert-butyl acrylate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, double
Process and be granulated in screw extruder, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm, most
Obtained antistatic thermoplastic elastomer (TPE) TPV b4 eventually.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 10.6MPa, elongation at break 442%, MFR are 1.1g/10min (10kg).
Embodiment 5
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 35% ethylene propylene diene rubber and be added in high-speed mixer, the ethylene propylene diene rubber
Mooney viscosity be 65,70% Third monomer content 4.2% of ethylene contents, and Third monomer be ethylidene-norbornene.So
30% isotactic polypropylene and 30% conductive black are once added afterwards, wherein the polypropylene melt flow rate is 4 ± 2, etc.
Advise index >=96%；Conductive black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm.So
After 1% stabilizer, 0.5% antioxidant is added, add 0.2% coupling agent, stir one minute, be eventually adding 2.5% lubricant,
It processes and is granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), revolving speed 300rpm obtains intermediate a5；
B), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a5, wherein crosslinking agent is isopropyl peroxide carbon
Tert-butyl acrylate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, double
Process and be granulated in screw extruder, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm, most
Obtained antistatic thermoplastic elastomer (TPE) TPV b5 eventually.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 12.7MPa, elongation at break 472%, MFR are 1.4g/10min (10kg).
Embodiment 6
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 20% ethylene propylene diene rubber and be added in high-speed mixer, the ethylene propylene diene rubber
Mooney viscosity be 65,70% Third monomer content 4.2% of ethylene contents, and Third monomer be ethylidene-norbornene.So
45% isotactic polypropylene and 30% conductive black are once added afterwards, wherein the polypropylene melt flow rate is 4 ± 2, etc.
Advise index >=96%；Conductive black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm.So
After 1% stabilizer, 0.5% antioxidant is added, add 0.2% coupling agent, stir one minute, be eventually adding 2.5% lubricant,
It processes and is granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), revolving speed 300rpm obtains intermediate a6；
B), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a6, wherein crosslinking agent is isopropyl peroxide carbon
Tert-butyl acrylate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, double
Process and be granulated in screw extruder, the setting of the temperature of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C,
180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm, most
Obtained antistatic thermoplastic elastomer (TPE) TPV b6 eventually.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 18.7MPa, elongation at break 617%, MFR are 1.5g/10min (10kg).
The comparative example each other of embodiment 4,5,6, it is main to illustrate different proportion polyolefin elastomer/polyolefin resin to mechanical property and electrical property
The influence of energy, performance is compared, as a result as shown in the table:
It is learnt by comparison, under based on carbon black additive amount the same terms, with the increase of polyolefin resin content, integral hardness is big
Width rises, and mechanical strength increases, but the same period does not increase electric conductivity, and embodiment 5 is that polyolefin elastomer/polyolefin resin ratio connects
When being closely 1 or so, resulting electric conductivity is best, thus illustrates that distribution of the carbon black in system is not present in merely a certain phase
It is interior, but have that part carbon black is deposited at polyolefin resin and the interface of polyolefin elastomer is inside.
Embodiment 7
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 35% ethylene propylene diene rubber and be added in high-speed mixer, the ethylene propylene diene rubber
Mooney viscosity be 65,70% Third monomer content 4.2% of ethylene contents, and Third monomer be ethylidene-norbornene.So
30% isotactic polypropylene and 30% conductive black are once added afterwards, wherein the polypropylene melt flow rate is 4 ± 2, etc.
Advise index >=96%；Conductive black DBP absorption value is 170-185ml/g, iodine absorption value is 360Mg/g, partial size 9-17nm.So
After 1% stabilizer, 0.5% antioxidant is added, add 0.2% coupling agent, stir one minute, be eventually adding 2.5% lubricant,
It processes and is granulated in double screw extruder after mediating one minute, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150
DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to machine
Head), revolving speed 300rpm obtains intermediate a7；
B), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a7, wherein crosslinking agent is cumyl peroxide；
Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double screw extruder
Middle processing is granulated, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C,
Antistatic is finally made in 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm
Thermoplastic elastomer (TPE) TPV b7.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
107Ω .cm, tensile strength 18.6MPa, elongation at break 360%, MFR are 2.0g/10min (10kg).
Embodiment 7 mainly substitutes main crosslinking agent, and the result that main crosslinking agent is only substituted under same recipe is as shown in the table:
It is learnt by comparison, two different main crosslinking agents respectively have a superiority and inferiority in the performance of mechanical property, and the main friendship in electric conductivity
Connection agent is that tert-butylperoxy isopropyl carbonate can obtain lower volume resistivity, and this is mainly due to main crosslinking agents in dynamic
While vulcanization, also to wherein polypropylene, there are degradations, and polypropylene segment is promoted to degrade, and further result in carbon black in system
Dispersion change, therefore, on properties of product, there is also influences for the selection of main crosslinking agent.
Embodiment 8
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 28% random polypropylene and be added in high-speed mixer, the melt polypropylene stream
Dynamic rate is 16 ± 3.Then 14% conductive black is added, the conductive black DBP absorption value is 380-460ml/g, iodine is inhaled
Receipts value is 950Mg/g, partial size 8-10nm.Then 1% stabilizer, 0.2% antioxidant is added, adds 0.3% coupling agent, stirs
It mixes one minute, is eventually adding 2% lubricant, process and be granulated in double screw extruder after mediating one minute, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200
DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 8；
B), 25% ethylene propylene diene rubber is added in conductive agglomerate 8 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 70, ethylene contents 70%, Third monomer content 5%, and Third monomer is ethylidene-norbornene.
Then 14% and the identical conductive black of step a) is added.Then 1% stabilizer is added, 0.2% antioxidant stirs one minute,
It is eventually adding 1.5% lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder heating zone
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
(sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate a8；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a8, wherein crosslinking agent is isopropyl peroxide carbon
Tert-butyl acrylate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, double
It processes and is granulated in screw extruder, in granulation process, 12% white oil, double screw extruder heating are added by liquid spout
The temperature in area is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180
DEG C (sequentially for from feed opening to head), revolving speed 260rpm, finally obtained antistatic thermoplastic elastomer (TPE) TPV b8.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 9.4MPa, elongation at break 419%, MFR are 17.4g/10min (10kg).
Embodiment 9
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 28% random polypropylene and be added in high-speed mixer, the melt polypropylene stream
Dynamic rate is 16 ± 3.Then 14% conductive black is added, the conductive black DBP absorption value is 170-185ml/g, iodine is inhaled
Receipts value is 360Mg/g, partial size 9-17nm.Then 1% stabilizer, 0.2% antioxidant is added, adds 0.3% coupling agent, stirs
It mixes one minute, is eventually adding 2% lubricant, process and be granulated in double screw extruder after mediating one minute, double screw extruder
The temperature of heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200
DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 9；
B), 25% ethylene propylene diene rubber is added in conductive agglomerate 9 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 70, ethylene contents 70%, Third monomer content 5%, and Third monomer is ethylidene-norbornene.
Then 14% and the identical conductive black of step a) is added.Then 1% stabilizer is added, 0.2% antioxidant stirs one minute,
It is eventually adding 1.5% lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder heating zone
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
(sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate a9；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate a9, wherein crosslinking agent is isopropyl peroxide carbon
Tert-butyl acrylate；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, double
It processes and is granulated in screw extruder, in granulation process, 12% white oil, double screw extruder heating are added by liquid spout
The temperature in area is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180
DEG C (sequentially for from feed opening to head), revolving speed 260rpm, finally obtained antistatic thermoplastic elastomer (TPE) TPV b9.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 107Ω .cm, tensile strength 12.7MPa, elongation at break 679%, MFR are 35.1g/10min (10kg).
Embodiment 10
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 28% random polypropylene and be added in high-speed mixer, the melt polypropylene stream
Dynamic rate is 16 ± 3.Then 14% conductive black is added, the conductive black DBP absorption value is 130-140ml/g, iodine is inhaled
Receipts value is 220Mg/g, partial size 15-25nm.Then 1% stabilizer, 0.2% antioxidant is added, adds 0.3% coupling agent,
Stirring one minute is eventually adding 2% lubricant, processes and is granulated in double screw extruder after mediating one minute, twin-screw extrusion
The temperature of machine heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200
DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 10；
B), 25% ethylene propylene diene rubber is added in conductive agglomerate 10 to be put into high-speed mixer together, the EPDM
The Mooney viscosity of rubber is 70, ethylene contents 70%, Third monomer content 5%, and Third monomer is ethylidene-norborneol
Alkene.Then 14% and the identical conductive black of step a) is added.Then 1% stabilizer is added, 0.2% antioxidant stirs one point
Clock is eventually adding 1.5% lubricant, processes and is granulated in double screw extruder after mediating one minute, double screw extruder heating
The temperature in area is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180
DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate a10；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate, wherein crosslinking agent is isopropyl peroxide carbonic acid
The tert-butyl ester；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double spiral shells
It processes and is granulated in bar extruder, in granulation process, 12% white oil, double screw extruder heating zone are added by liquid spout
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
Antistatic thermoplastic elastomer (TPE) TPV b10 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm, the volume resistance of material using vertical injection molding machine
Rate is 107Ω .cm, tensile strength 10.3MPa, elongation at break 600%, MFR are 41.7g/10min (10kg).
Comparative example, main elaboration select the conductive black of different indexs to the shadow of mechanical property and electrical property to embodiment 8,9,10 each other
It rings, performance is compared, as a result as shown in the table:
It is learnt by comparison, carbon black selects index DBP absorption value, iodine absorption value to respectively represent the aggregation extent and specific surface for levying carbon black
Product, the above numerical value is higher can actually to reflect that electric conductivity is better in thermoplastic elastomer system, but the conduction of excessively high numerical value
There is negative effect to whole mechanical property in carbon black, and from considering in price, the electrical property added value unilaterally promoted
The promotion of overall value can not be driven, therefore moderate conductive black is selected just to be able to achieve optimal use value.
Embodiment 11
The process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account, detailed process is as follows:
A), measured according to weight ratio, first weigh 1% coupling agent, be put into ethanol solution and be stirred, and it is weak for adjusting PH
Alkalinity makes its hydrolysis, then weighs 20% conductive black, and the conductive black DBP absorption value is 170-185ml/g, iodine absorbs
Value is 360Mg/g, partial size 9-17nm, is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, and obtains pretreatment powder
Afterwards, it weighs 10% conductive black and 20% random polypropylene is added in high-speed mixer, the polypropylene melt flow rate
It is 65 ± 10.Then 2% dispersing agent is added, stirring is processed in double screw extruder after mediating and is granulated, twin-screw extrusion
The temperature of machine heating zone is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200
DEG C, 190 DEG C (sequentially for from feed opening to head), revolving speed 300rpm obtains conductive agglomerate 11；
B) 25% ethylene propylene diene rubber is added in conductive agglomerate 11 to be put into high-speed mixer together, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-norborneol
Alkene.Then be added 5% nitrile rubber powder, the nitrile rubber Mooney viscosity is 57, acrylonitrile content 33%, then plus
Enter 5% maleic anhydride grafting ethylene propylene diene rubber, 5% maleic anhydride inoculated polypropylene, the identical conductive charcoal of 10% and step a)
It is black.Then it is added, 0.2% antioxidant, stirs one minute, be eventually adding 1% dispersing agent, in twin-screw extrusion after mediating one minute
It processes and is granulated in machine, the temperature setting of double screw extruder heating zone are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185
DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), revolving speed 260rpm obtains intermediate
a11；
C), 0.2% crosslinking agent and 0.5% assistant crosslinking agent are added in intermediate, wherein crosslinking agent is isopropyl peroxide carbonic acid
The tert-butyl ester；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in double spiral shells
It processes and is granulated in bar extruder, in granulation process, 15% white oil, double screw extruder heating zone are added by liquid spout
Temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C
Antistatic thermoplastic elastomer (TPE) TPV b11 is finally made in (sequentially for from feed opening to head), revolving speed 260rpm.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistance of material is 105
Ω .cm, tensile strength 8.2MPa, elongation at break 500%, MFR are 14.5g/10min (5kg).
11 comparative example 1 of embodiment, although tensile strength, elongation at break and fluidity of molten are slightly decreased, its volume
Resistivity reduces 1 order of magnitude, shows to increase product polarity energy in non-polar rubber inner part graft modification polar rubber
Enough effectively improve product electric conductivity.
Embodiment 12
A), measured according to weight ratio, first weigh 1% coupling agent, be put into ethanol solution and be stirred, and it is weak for adjusting PH
Alkalinity makes its hydrolysis, then weighs 25% conductive black, and the conductive black DBP absorption value is 170-185ml/g, iodine absorbs
Value is 360Mg/g, partial size 9-17nm, is added thereto stirring, and then heating water bath makes ethyl alcohol volatilize, and obtains pretreatment powder
Afterwards, it then weighs in 7% random polypropylene addition high-speed mixer, the polypropylene melt flow rate is 16 ± 3.Then plus
Enter 7% conductive black, 0.1% stabilizer, 0.1% antioxidant be added, add 0.2% coupling agent, stir one minute, finally plus
Enter 0.2% lubricant, process and be granulated in double screw extruder after mediating one minute, the temperature of double screw extruder heating zone is set
Be set to: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C (are sequentially
From feed opening to head), revolving speed 300rpm obtains conductive agglomerate 12；
B), 25% hydrogenated styrene-butadiene block copolymer is added in conductive agglomerate 11 to be put into high-speed mixer together,
The number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene-content 35%.Then it is added
18% with the identical conductive black of step a).Then be added 0.1% stabilizer, 0.1% antioxidant stirs one minute, finally plus
Enter 0.2% lubricant, 32% white oil is processed in double screw extruder after mediating one minute and is granulated, double screw extruder heating
The temperature in area is set are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 185 DEG C, 180
DEG C (sequentially for from feed opening to head), revolving speed 260rpm, finally obtained antistatic thermoplastic elastomer (TPE) TPE 12.
Above-mentioned material under the conditions of 180 DEG C, is molded the thin slice of thickness 3mm using vertical injection molding machine, and the volume resistivity of material is
106Ω .cm, tensile strength 10.3MPa, elongation at break 574%, MFR are 9.6g/10min (10kg).
Ethylene propylene diene rubber (EPDM) described in above-described embodiment 1,2,3 and 11, polyolefin resin polypropylene (PP) it is micro-
Shown in enlarged drawing figure attached drawing 1, the micro- enlarged diagram for activating carbon black is as shown in Fig. 2.
Comparative example 1
Common thermoplastic's elasticity preparation, comprising the following steps:
A), measured according to weight ratio, first weigh 30% ethylene propylene diene rubber and be added in high-speed mixer, the ethylene-propylene-diene monomer
The Mooney viscosity of glue is 51, ethylene contents 67%, Third monomer content 4.7%, and Third monomer is ethylidene-norborneol
Alkene.Then 25% random polypropylene is added, wherein the polypropylene melt flow rate is 65 ± 10；Then 20% carbon is added
Sour calcium, 1.3% stabilizer, 0.4% antioxidant stir one minute, are eventually adding 2.5% lubricant, double after mediating one minute
It processes and is granulated in screw extruder, obtain intermediate product；
B), 0.2% crosslinking agent and 0.5% assistant crosslinking agent is added in the midbody product, wherein crosslinking agent is that peroxidating two is different
Propyl benzene；Assistant crosslinking agent is diphenyl-methane maleimide.Then 0.1% release agent is added, after mediating 1-2 minutes, in twin-screw
It processes and is granulated in extruder, a kind of common thermoplastic's elastomer 1 is finally made.
The performance of elastomer common in antistatic elastomer obtained and comparative example is compared, as a result as shown in table 1 below,
It is as shown in table 2 below additionally individually to list the performance comparison of antistatic elastomer after weathering:
1 elastomer performance contrast test result of table
The performance test results after 2 elastomer degradation of table
As can be seen from the table, antistatic elastomer 1 is compared with conventional elastomers 1, and conduction significantly improves, and tensile strength,
Compared to the inorganic filler that equivalent is filled, it is original that antistatic elastomer can more take into account elastomer for elongation at break and tearing strength etc.
Mechanical property.Meanwhile antistatic elastomer 7 days and 15 days heat ageing the result shows that product after heat ageing with it is unaged
It is not much different, shows good resistance to ag(e)ing.
Comparative example 2
Common thermoplastic's elasticity preparation, comprising the following steps:
A), measured according to weight ratio, first weigh 25% hydrogenated styrene-butadiene block copolymer and be added in high-speed mixer,
The number-average molecular weight 260000 of the hydrogenated styrene-butadiene block copolymer, styrene-content 35%.Then it is added
Polypropylene melt flow rate described in 7% random polypropylene is 16 ± 3.Then be added 25% calcium carbonate, 0.3% stabilizer,
0.3% antioxidant is eventually adding 0.2% lubricant, and 32% white oil is processed in double screw extruder after mediating one minute and made
Grain, double screw extruder heating zone temperature setting are as follows: 80 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C,
185 DEG C, 185 DEG C, 185 DEG C, 180 DEG C (sequentially for from feed opening to head), a kind of common thermoplastic is finally made in revolving speed 260rpm
Property elastomer 2.
The performance of elastomer common in antistatic elastomer 12 obtained and comparative example is compared, as a result such as the following table 3 institute
Show, it is as shown in table 4 below additionally individually to list the performance comparison of antistatic elastomer after weathering:
3 elastomer performance contrast test result of table
The performance test results after 4 elastomer degradation of table
As can be seen from the table, antistatic elastomer 12 is compared with conventional elastomers 2, and conduction significantly improves, gained tensile strength,
Elongation at break and tearing strength etc. lose more mechanical property compared to the inorganic filler that equivalent is filled, antistatic elastomer
It is low.For antistatic elastomer in 7 days and 15 days heat ageing results compared to comparative example 1 and the obtained table of corresponding elastomer 1
Existing relatively poor, reason is antistatic elastomer 12 for TPE, and there are a large amount of white oils in system, white by long-time aging
There is Evaporation Phenomenon in oil, therefore existing on electrical property and mechanical property influences at high temperature, and existing influence enthusiasm is greater than passiveness
Property, i.e., it is above-mentioned by aging post-tensioning intensity and stretching strength, and volume resistivity is lower compared with before aging, electric conductivity is more preferably.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technical side described in the invention
Case；Therefore, although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, ability
Domain it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement；And all do not depart from this hair
The technical solution and its improvement of bright spirit and scope, should all cover within the scope of the claims of the present invention.
Claims (10)
1. a kind of thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity, which is characterized in that in parts by weight, including it is following
Component:
30-40 parts of non-polar rubber,
20-30 parts of polyolefin resin,
20-30 parts of conducting medium,
Maleic anhydride is grafted non-polar rubber 0-10 parts,
0-10 parts of maleic anhydride stem grafting polyolefin resin,
0-10 parts of polar rubber,
0.08-0.8 parts of crosslinking agent,
0.6-6 parts of assistant crosslinking agent,
0-40 parts of white oil,
0-20 parts of inorganic filler,
0-0.5 part of antioxidant,
0-5 parts of dispersing agent,
0-0.5 parts of light stabilizer,
0-5 parts of coupling agent,
0-1 parts of release agent.
2. the thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity according to claim 1, which is characterized in that the friendship
Connection agent is one of tert-butylperoxy isopropyl carbonate, cumyl peroxide or octyl phenolic or any number of group
It closes, the inorganic filler is one of calcium carbonate, talcum powder or white carbon black or any number of combination, and the assistant crosslinking agent is hexichol
Methane maleimide, triisopropyl isocyanates, allyl methacrylate, ethylene glycol dimethacrylate or protochloride
One of tin or any number of combination.
3. the thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity according to claim 1, which is characterized in that described non-
Polar rubber is the combination of one or both of polyolefin elastomer or styrene block copolymers, and the maleic anhydride grafting is non-
Polar rubber is the polyolefin elastomer of modified by maleic acid anhydride graft or the styrene block copolymers of modified by maleic acid anhydride graft
One or both of combination, the polar rubber be one or both of nitrile rubber or neoprene combine.
4. the thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity according to claim 1, which is characterized in that described
Polyolefin resin be one of polyethylene, polypropylene or polyethylene and polyacrylic mixture or any number of combination, it is described
Maleic anhydride stem grafting polyolefin resin be the polyethylene of modified by maleic acid anhydride graft, modified by maleic acid anhydride graft polypropylene and
One of polyethylene and polypropylene of modified by maleic acid anhydride graft or any number of combination.
5. taking into account the thermoplastic elastomer (TPE) of mechanical property and electric conductivity according to claim 3, which is characterized in that described poly-
Olefinic rubber is the ethylene propylene diene rubber of Mooney viscosity 20-100, and the styrene block copolymers is number-average molecular weight
The styrene-butadiene-styrene or hydrogenated styrene-butadiene block copolymer of 50000-300000, it is described
Polar rubber is the nitrile rubber or neoprene of Mooney viscosity 20-100.
6. the thermoplastic elastomer (TPE) according to claim 1 for taking into account mechanical property and electric conductivity, which is characterized in that the conduction
Medium be partial size be 10-20nm, the thermal cracking carbon black of meta-alkalescence；The conducting medium is DBP absorption value 300-500ml/g, iodine
Absorption value 800-1000Mg/g, specific surface area 750-1100m2/ kg, resistivity≤0.5% Ω .m.
7. the thermoplastic elastomer (TPE) for taking into account mechanical property and electric conductivity according to claim 1, which is characterized in that the idol
Connection agent is titanate coupling agent, silane coupling agent or one of titanate coupling agent and silane coupling agent or any number of group
It closes.
8. taking into account the process for preparation of thermoplastic elastomer of mechanical property and electric conductivity, it is characterised in that: when non-polar rubber is poly-
When olefinic rubber, comprising the following steps:
A), conducting medium is added in coupling agent solution and will be infiltrated, adjust pH value to being in alkalescent, heating water bath stirring, dry
To activation conducting medium；
B), ratio according to claim 1 by polyolefin resin and conducting medium after mixing, dispersing agent is added, through molten
After melting mixing facilities melt blending, conductive agglomerate is obtained；
C), by the resulting conductive agglomerate of step B), polyolefin elastomer, polar rubber, modified by maleic acid anhydride graft polyolefin rubber
Glue, maleic acid change grafted polyolefinic resin, conducting medium, inorganic filler, antioxidant, dispersing agent, light stabilizer mixing
After uniformly, through melting mixing equipment mixing granulation, intermediate product is both obtained；
D), the intermediate product, white oil, crosslinking agent, assistant crosslinking agent, dispersant is uniform, in melting mixing equipment into
After Mobile state vulcanization, antistatic thermoplastic elastomer (TPE) is made.
9. taking into account the process for preparation of thermoplastic elastomer of mechanical property and electric conductivity, it is characterised in that: when synthetic rubber is benzene second
When alkenes block copolymer, comprising the following steps:
A), conducting medium is added in coupling agent solution and will be infiltrated, adjust pH value to being in alkalescent, heating water bath stirring, dry
To activation conducting medium；
B), in proportion by polyolefin resin and conducting medium after mixing, be added dispersing agent, melted through melting mixing equipment
After blending, conductive agglomerate is obtained；
C), by the resulting conductive agglomerate of step B), styrene block copolymers, polar rubber, modified by maleic acid anhydride graft
The styrene block copolymers of modified by maleic acid anhydride graft, maleic acid change grafted polyolefinic resin, conducting medium, inorganic
Filler, white oil, antioxidant, dispersant are uniform, and after carrying out dynamic vulcanization in melting mixing equipment, antistatic thermoplastic is made
Property elastomer.
10. the process for preparation of thermoplastic elastomer of mechanical property and electric conductivity is taken into account according to claim 8 or 9,
Be characterized in that: the melting mixing equipment is double screw extruder, and process conditions are 160 ~ 220 DEG C of temperature, revolving speed 200
~ 320rpm；
Above-mentioned antistatic thermoplastic elastic material is molded 3 mm's of thickness using vertical injection molding machine under the conditions of 180 DEG C
Print prepares tensile bars using universal sampling machine, the stretching for measuring material is strong using the volume resistance of resistance instrument measurement sample
The processing flowability of degree and elongation at break, material passes through the melt flow under the conditions of 230 DEG C of measuring temperature, load 5/10kg
Index M FR is moved to characterize.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234347A (en) * | 2020-02-21 | 2020-06-05 | 南京工业大学 | Method for preparing conductive thermoplastic elastomer by combining prefabricated master batch with phase structure regulation and control |
| CN112111159A (en) * | 2020-09-18 | 2020-12-22 | 苏州雷朗新材料科技有限公司 | High-temperature vulcanized silicone rubber with conductivity and ceramic property and preparation method thereof |
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
| WO2022175351A1 (en) * | 2021-02-18 | 2022-08-25 | Borealis Ag | Upgraded polyolefin for electrical components |
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2019
- 2019-04-19 CN CN201910317793.2A patent/CN110183783A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234347A (en) * | 2020-02-21 | 2020-06-05 | 南京工业大学 | Method for preparing conductive thermoplastic elastomer by combining prefabricated master batch with phase structure regulation and control |
| CN111234347B (en) * | 2020-02-21 | 2022-04-22 | 南京工业大学 | Method for preparing conductive thermoplastic elastomer by combining prefabricated master batch with phase structure regulation and control |
| CN112111159A (en) * | 2020-09-18 | 2020-12-22 | 苏州雷朗新材料科技有限公司 | High-temperature vulcanized silicone rubber with conductivity and ceramic property and preparation method thereof |
| CN112194854A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | Low-dielectric-property composite thermoplastic elastomer and preparation method thereof |
| WO2022175351A1 (en) * | 2021-02-18 | 2022-08-25 | Borealis Ag | Upgraded polyolefin for electrical components |
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Application publication date: 20190830 |