CN102653613B - Conductive fully-vulcanized thermoplastic elastomer and preparation method thereof - Google Patents
Conductive fully-vulcanized thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a conductive fully-vulcanized thermoplastic elastomer and a preparation method thereof and relates to the technical field of fully-vulcanized thermoplastic elastomers. The fully-vulcanized thermoplastic elastomer is obtained by one-time melting and blending of components including rubber particles with mean grain size of 0.02-1 mu m and a crosslinking structure, carbon nanotubes used as a conductive filler, thermoplastics and the like. The conductive fully-vulcanized thermoplastic elastomer prepared by the method is low in filling volume of the conductive filler and excellent in comprehensive performance, and can be prepared by using a common rubber and plastic processing method and used for preparing decorative materials for electronic production equipment, tools, electronic instruments, instrument shells and dust-free production workshops with antistatic, anti-interference of electromagnetic wave and dust-free requirements.
Description
Technical field
The present invention relates to fully sulfurized thermoplastic elastomer, further say, the present invention relates to fully sulfurized thermoplastic elastomer of a kind of conduction and preparation method thereof.
Background technology
Fully sulfurized thermoplastic elastomer is the type material of the eighties development.It has plastics and rubber property concurrently: show at normal temperatures rubber snappiness, and again can plasticizing forming under high temperature.Intensity, elasticity, thermotolerance and the incompressible tension set of fully sulfurized thermoplastic elastomer all will improve a lot than uncrosslinked thermoplastic elastomer.Meanwhile, chemicals-resistant and processing stability have clear improvement, and rubber plastic blend ratio can change in a big way, make material in performance, have larger adjusting leeway.Therefore be of wide application.In conventional art, fully sulfurized thermoplastic elastomer is to be prepared with dynamic vulcanization process under certain conditions by the thermoplastics of elastomerics and rigidity.
(applying date is June 15 calendar year 2001 to the applicant's Chinese patent CN1184265C, priority date is on June 15th, 2000, patent No. ZL01801655.3), provide a kind of particle diameter of rubber phase controlled, profile is spherical fully sulfurized thermoplastic elastomer of class and preparation method thereof.This fully sulfurized thermoplastic elastomer is to utilize conventional blending method in rubber and plastic processing, and fully vulcanized powder rubber and plastics are made by rubber plastic blend equipment blend granulation.The weight ratio of fully vulcanized powder rubber and plastics is 30: 70～75: 25, preferably 50: 50-75: 25.Wherein rubber components is the rubber particles with crosslinking structure, and its median size is 0.02 μ m～1 μ m, is preferably 0.05 μ m～0.5 μ m, and more excellent is 0.05 μ m～0.2 μ m.The gel content of this kind of rubber particles is 60% weight or higher, can be selected from the prepared fully vulcanized powder rubber of International Patent Application WO 01/40356 of submitting on September 18th, 2000 according to the applicant, comprise at least one of following fully vulcanized powder rubber: form of finely divided powder, mehtod natural rubber, form of finely divided powder, mehtod styrene-butadiene rubber(SBR), form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, Vulcanized Powdered Nitrile Rubber, form of finely divided powder, mehtod carboxy nitrile rubber, form of finely divided powder, mehtod polybutadiene rubber, form of finely divided powder, mehtod chloroprene rubber, fully sulfurized silicon rubber powder, form of finely divided powder, mehtod acrylic elastomer, form of finely divided powder, mehtod vinylpyridiene-styrene-butadiene rubber, form of finely divided powder, mehtod polyisoprene rubber, form of finely divided powder, mehtod isoprene-isobutylene rubber, form of finely divided powder, mehtod thiorubber, form of finely divided powder, mehtod Acrylester Butadiene Rubber, form of finely divided powder, mehtod urethanes or form of finely divided powder, mehtod viton etc., the plastics of this kind of fully sulfurized thermoplastic elastomer comprise at least one in following material: polypropylene, polyethylene, polymeric amide, polyvinyl chloride, urethane, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene sulfide, polyimide or polysulfones etc.
This fully sulfurized thermoplastic elastomer is to utilize common blending method in rubber and plastic processing, will comprise that plastics and fully vulcanized powder rubber component are by rubber plastic blend equipment, melt blending granulation under the common processing temperature of plastics and make fully sulfurized thermoplastic elastomer.
The fully sulfurized thermoplastic elastomer that this patent CN1184265C provides, compared with the standby fully sulfurized thermoplastic elastomer of conventional dynamic sulfuration legal system, the particle diameter of its rubber phase and gel content controllability are good, have good mechanical property.Especially there is higher whiteness value, be easy to make light goods, be also easy to dyeing and make the goods of other color.The method of the described fully sulfurized thermoplastic elastomer of preparation that this patent application simultaneously provides is comparatively easy.The method is different from dynamic vulcanization process, and it uses general rubber plastic blend equipment and does not need specific installation, and technique is simple, and processing condition are easy to control, good for particle diameter and the degree of crosslinking controllability of rubber phase.
But fully sulfurized thermoplastic elastomer prepared by this patent CN1184265C does not have conductivity, cannot adapt to the requirement of the special applications with conduction requirement.
Summary of the invention
Applicant is found under study for action, when thermoplastics as external phase and the rubber particles with crosslinking structure if fully vulcanized powder rubber is as disperse phase, when the method for employing blend is prepared fully sulfurized thermoplastic elastomer, because fully vulcanized powder rubber vulcanizes before blend, it in Blending Processes, is disperse phase always, and can in plastic substrate, reach dispersed, at this moment add a small amount of electro-conductive material as carbon nanotube, the carbon nanotube adding will can not disperse or be wrapped in rubber phase, but be dispersed in plastics external phase and be distributed between rubber domain.As long as add so a small amount of carbon nanotube, just can form effective conductive path, thereby make prepared thermoplastic elastomer there is good conductivity, its original other performances are not affected substantially simultaneously.
The object of this invention is to provide a kind of conduction fully sulfurized thermoplastic elastomer.This conduction fully sulfurized thermoplastic elastomer, has satisfactory electrical conductivity.
Another object of the present invention is to provide a kind of preparation method of conducting electricity fully sulfurized thermoplastic elastomer.The method is used general rubber plastic blend equipment, and disposable to plastics, rubber particles and conductive filler material blend is prepared to conduction fully sulfurized thermoplastic elastomer, and technique is simple, and conductive filler material usage quantity is few.
Fully sulfurized thermoplastic elastomer of the present invention comprises the following component of blend:
A. thermoplastics; B. there is the rubber particles of crosslinking structure; C. conductive filler material; The median size of the rubber particles of wherein said components b is 0.02-1 μ m, and gel content is 60% weight or higher; The conductive filler material of described amount of component b is carbon nanotube.
The Micro of conduction fully sulfurized thermoplastic elastomer of the present invention is: the thermoplastics of described component a is external phase, and the rubber particles of described components b is disperse phase, and the carbon nanotube dispersed of described amount of component b is in external phase and be distributed between rubber particles.
Such Micro, utilizes a small amount of carbon nanotube, just can form effective conductive path, thereby makes prepared fully sulfurized thermoplastic elastomer have good conductivity, and its original other performances are not affected substantially simultaneously.And the size of carbon nanotube is not had to special requirement.
Compared to existing technology, carbon nanotube is in the time of thermoplastic elastic material prepared by modified plastics or polymerization process, because the volume that the rubber particles not vulcanized produces as rubber phase is got rid of effect, do not there is this special Micro, carbon nanotube is distributed in the various piece of plastic substrate, or in the time of modified thermoplastic elastomer, be dispersed in the external phase and disperse phase of thermoplastic elastomer simultaneously, cause carbon nanotube need to add to after certain amount, could in matrix, form enough conductive paths, just can there is electroconductibility.And because addition is large, also can have influence on other mechanical propertys of matrix.Even also needing has specific requirement could realize the modification of conduction aspect to the size of carbon nanotube.
Conduction fully sulfurized thermoplastic elastomer of the present invention, the weight ratio of the thermoplastics of the rubber particles of wherein said components b and component a is 30: 70～75: 25, is preferably 50: 50-75: 25.The content of the conductive filler material of amount of component b is take the rubber particles of components b and the thermoplastics gross weight of component a as 100 parts, and its parts by weight are 0.5～10 part, are preferably 0.5～7 part.
Components b described in conduction fully sulfurized thermoplastic elastomer of the present invention, has the rubber particles of crosslinking structure, is preferably the rubber particles of equal phase structure, and its median size is 0.02～1 μ m, is preferably 0.05～0.5 μ m, and more excellent is 0.05～0.2 μ m.Its gel content is in 60% weight or higher, preferably 75% weight or higher.In the fully sulfurized thermoplastic elastomer of preparation, the gel content of rubber phase is this kind and has the gel content of the rubber particles of crosslinking structure itself thus.
In conductivity type fully sulfurized thermoplastic elastomer of the present invention, as the rubber kind of disperse phase, without any restriction, it can select at least one of following rubber: natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polybutadiene rubber, silicon rubber, chloroprene rubber, acrylic elastomer, vinylpyridiene-styrene-butadiene rubber, polyisoprene rubber, isoprene-isobutylene rubber, thiorubber, Acrylester Butadiene Rubber, urethanes or viton.
The rubber particles with crosslinking structure of the above components b is preferably the prepared fully vulcanized powder rubber of International Patent Application WO 01/98395 (priority date on June 15th, 2000) of submitting June 15 calendar year 2001 in International Patent Application WO 01/40356 (priority date on December 3rd, 1999) and the applicant of submission on September 18th, 2000 according to the applicant.In preparation process, preferentially select at least one of following fully vulcanized powder rubber: form of finely divided powder, mehtod natural rubber, form of finely divided powder, mehtod styrene-butadiene rubber(SBR), form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, Vulcanized Powdered Nitrile Rubber, form of finely divided powder, mehtod carboxy nitrile rubber, form of finely divided powder, mehtod polybutadiene rubber, form of finely divided powder, mehtod chloroprene rubber, fully sulfurized silicon rubber powder, form of finely divided powder, mehtod acrylic elastomer, form of finely divided powder, mehtod vinylpyridiene-styrene-butadiene rubber, form of finely divided powder, mehtod polyisoprene rubber, form of finely divided powder, mehtod isoprene-isobutylene rubber, form of finely divided powder, mehtod thiorubber, form of finely divided powder, mehtod Acrylester Butadiene Rubber, form of finely divided powder, mehtod urethanes or form of finely divided powder, mehtod viton etc.This kind of fully vulcanized powder rubber refers to that gel content reaches 60% weight or higher, and more excellent is 75% weight or higher, dry after without with separant being free flowable rubber micro mist.In this patent application, the median size of powdered rubber is 0.02～1 μ m, is preferably 0.05～0.5 μ m, and more excellent is 0.05～0.2 μ m.Each particulate in this kind of fully vulcanized powder rubber is homogeneous phase, and single particulate is all homogeneous on composition, does not find the phenomenon of layering, point equal uneven phase under the observation of existing microtechnique in particulate.This powdered rubber is by fixing corresponding rubber latex cross-linking radiation by rubber particles particle diameter.
Above-described rubber particles can also adopt Chinese patent CN1353131A according to the applicant, and (applying date is on November 3rd, 2000, patent No. ZL00130386.4) prepared cross-linked powdered rubber, it comprises following cross-linked powdered rubber at least one: cross-linked powdery styrene-butadiene rubber(SBR) or cross-linked powdery polybutadiene rubber etc.This kind of cross-linked powdered rubber is a kind of take cross-linking type synthetic rubber latex as raw material, the powdered rubber that drying obtains.This cross-linked powdered rubber does not need to add separant to get final product unrestricted flow.In this patent CN1353131, the median size of powdered rubber is 0.05～0.3 μ m.Its gel content is consistent with the gel content of the cross-linking type synthetic rubber latex as raw material, is 80% weight or higher, is preferably 85% weight or higher.Each particulate in this cross-linked powdered rubber is homogeneous phase, and single particulate is all homogeneous on composition, does not find the phenomenon of layering, point equal uneven phase under the observation of existing microtechnique in particulate.
The elastomeric component a thermoplastics of the fully sulfurized statue of conduction of the present invention can be selected various thermoplasticss in prior art, preferably includes at least one in following polymkeric substance and multipolymer thereof: the graft modification thing (as grafted polyethylene, graft polypropylene etc.) of polypropylene, polyethylene, polymeric amide, polyvinyl chloride, urethane, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene sulfide, polyimide, polysulfones etc. or above thermoplastics.
The amount of component b conductive filler material conducting electricity in fully sulfurized thermoplastic elastomer as the present invention, it is selected from carbon nanotube, comprises Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes or its mixture.Preferably from multi-walled carbon nano-tubes.The size of described carbon nanotube there is no particular requirement, but according to existing market situation, and draw materials conveniently, it is that 0.4～500nm, mean length are that 0.1～1000 μ m, length-to-diameter ratio are 0.25～2.5 × 10 that general carbon nanotube is selected from mean diameter
6carbon nanotube, be preferably that 1～50nm, mean length are that 1～50 μ m, length-to-diameter ratio are 20～1 × 10 from mean diameter
4the carbon nanotube of carbon nanotube.
In the composition of conduction fully sulfurized thermoplastic elastomer of the present invention, can also include some auxiliary agents conventional in fully sulfurized thermoplastic plastic working process as oxidation inhibitor, tinting material, processing aid etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The preparation method of conduction fully sulfurized thermoplastic elastomer of the present invention is:
Utilize common melt-blending process in rubber and plastic processing, the thermoplastics of the above-described component a of the present invention will be included, the rubber particles with crosslinking structure and the conductive filler material of amount of component b etc. of components b in interior component by common rubber plastic blend equipment, a melt blending and make the fully sulfurized plastics elastomer of this conductivity type.
In preparation process, the blending temperature of material is the common processing temperature of thermoplastics, should in the scope of its decomposition, select not only guaranteeing the complete melting of plastics but also can not make.In addition,, according to processing needs, can in blend material, add in right amount the conventional auxiliary agent of plastic working.In Blending Processes, each components such as described rubber particles, conductive filler material and thermoplastics can be added simultaneously and in melt blending equipment, carried out melt blending by modes such as metered charge; Also can first pass through general mixing equipment, in advance described each component be mixed, and then through rubber plastic blend equipment, a melt blending is extruded and obtained described fully sulfurized thermoplastic elastomer.
The rubber plastic blend equipment using in preparation method of the present invention can be mill, Banbury mixer, single screw extrusion machine, twin screw extruder or torque rheometer etc.Described material mixing equipment is selected from homogenizer of the prior art, kneader etc. mechanical mixing equipment.
Conduction fully sulfurized thermoplastic elastomer of the present invention, adopts the method for a melt blending of component such as rubber particles, thermoplastics and conductive filler material with crosslinking structure is made.Because rubber phase has just had crosslinking structure before preparation, in preparation process, be disperse phase always, in Blending Processes, can in plastics external phase, be uniformly dispersed, conductive filler material can not disperse or be wrapped in rubber phase, but be dispersed in plastics external phase, be distributed between rubber particles.So only need little amount conductive filler material just can form effective conductive path, and prepare the fully sulfurized thermoplastic elastomer with excellent conductive performance.This fully sulfurized thermoplastic elastomer has good over-all properties simultaneously.Conduction fully sulfurized thermoplastic elastomer prepared by the present invention can make there is anti-electrostatic, anti electromagnetic wave disturbs and the finishing material of electronic production equipment, instrument, electronic instrument and meter shell and the dustless production plant of dustless requirement.Common rubber plastic blend equipment for this preparation method, utilize common melt blending extrusion molding preparation, under conventional blending technology condition, prepare conduction fully sulfurized thermoplastic elastomer with rubber particles and the conductive filler material with crosslinking structure.So its technique is simple, equipment cost is low, processing characteristics is improved, the goods conductive filler material loading level that processing condition are easy to control, gained is low, is applicable to the requirement of industrialized mass.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) picture of the fully sulfurized thermoplastic elastomer Micro that makes of embodiment 13.
Specific implementation method
Further described the present invention with embodiment below, but scope of the present invention is not subject to the restriction of these embodiment.Scope of the present invention is determined by accompanying claims.
Embodiment 1
To entirely vulcanize butylbenzene powdered rubber (Beijing Chemical Research Institute of China Petrochemical Industry, VP101A, gel content 84%wt, median size 100nm), carbon nanotube (Beijing Tiannai Science and Technology Co., Ltd, FloTube 9000, multi-walled carbon nano-tubes, mean length 10 μ m, mean diameter 11nm), linear low density polyethylene (asphalt in Shenli Refinery of China Petrochemical Industry produces, the trade mark 7042), antioxidant 1010 (Switzerland vapour Ba Jiaji production) and 168 (Switzerland vapour Ba Jiaji productions) fully mix in stirrer.Wherein fully vulcanized powder rubber and poly weight ratio are 60/40, and carbon nanotube is 3/100 with the gross weight ratio of polyethylene and fully vulcanized powder rubber, and antioxidant 1010 and 168 is respectively 0.2% and 0.4% of powdered rubber and poly gross weight.Use afterwards Branbender torque rheometer melt blending, blend oil bath temperature and rheometer revolution are set as 200 ℃ and 60 rpms (rpm), when material plasticizing evenly after discharging.Gained sample, with two roller mills (temperature is made as 200 ℃) in flakes, is made standard batten by material by compression molding, carries out properties test, and the conduction recording is vulcanized styrene-butadiene rubber(SBR)/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Embodiment 2
Except the gross weight ratio of carbon nanotube and polyethylene and full sulfuration butylbenzene powdered rubber be 4/100 mix, all the other are all identical with embodiment 1, the conductivity type recording vulcanizes styrene-butadiene rubber(SBR)/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Embodiment 3
Except the gross weight ratio of carbon nanotube and polyethylene and full sulfuration butylbenzene powdered rubber be 5/100 mix, all the other are all identical with embodiment 1, the conductivity type recording vulcanizes styrene-butadiene rubber(SBR)/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Embodiment 4
Except the gross weight ratio of carbon nanotube and polyethylene and full sulfuration butylbenzene powdered rubber be 6/100 mix, all the other are all identical with embodiment 1, the conductivity type recording vulcanizes styrene-butadiene rubber(SBR)/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Comparative example 1
Except not adding carbon nanotube, other are identical with embodiment 1, and experimental result is listed in table 1.
Embodiment 5
Be 40/60 except entirely vulcanizing butylbenzene powdered rubber and poly weight ratio, all the other are all identical with embodiment 2, and the conductivity type recording vulcanizes butylbenzene/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Comparative example 2
Except not adding carbon nanotube, other are identical with embodiment 5, and experimental result is listed in table 1.
Embodiment 6
Be 50/50 except entirely vulcanizing butylbenzene powdered rubber and poly weight ratio, all the other are all identical with embodiment 2, and the conductivity type recording vulcanizes butylbenzene/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Comparative example 3
Except not adding carbon nanotube, other are identical with embodiment 6, and experimental result is listed in table 1.
Embodiment 7
Be 70/30 except entirely vulcanizing butylbenzene powdered rubber and poly weight ratio, all the other are all identical with embodiment 2, and the conductivity type recording vulcanizes butylbenzene/rubber/polythene thermoplastic elastomer entirely, and the results are shown in Table 1.
Comparative example 4
Except not adding carbon nanotube, other are identical with embodiment 7, and experimental result is listed in table 1.
Table 1
Embodiment 8
To entirely vulcanize carboxyl butyronitrile powdered rubber (Beijing Chemical Research Institute of China Petrochemical Industry, VP501, gel content 91%wt, median size 90nm), carbon nanotube (with embodiment 1), polypropylene (blue star Tianjin Chemical Co., Ltd., No. 0 PP Pipe Compound, homo-polypropylene), antioxidant 1010 (Switzerland vapour Ba Jiaji production) and 168 (Switzerland vapour Ba Jiaji productions) fully mix in stirrer.Wherein entirely vulcanizing carboxyl butyronitrile powdered rubber and polyacrylic weight ratio is 70/30, carbon nanotube is 7/100 with the gross weight ratio of polypropylene and full sulfuration carboxyl butyronitrile powdered rubber, and antioxidant 1010 and 168 is respectively 0.2% and 0.4% of powdered rubber and polyacrylic gross weight.Use afterwards Branbender torque rheometer melt blending, blend oil bath temperature and rheometer revolution are set as 210 ℃ and 70 rpms (rpm), when material plasticizing evenly after discharging.Gained sample, with two roller mills (temperature is made as 200 ℃) in flakes, is made standard batten by material by compression molding, carries out properties test, and the conduction recording is vulcanized carboxy nitrile rubber/polypropylene thermoplastic elastomer entirely, and the results are shown in Table 2.
Embodiment 9
Except the gross weight ratio of carbon nanotube and polypropylene and full sulfuration carboxyl butyronitrile powdered rubber be 0.5/100 mix, all the other are all identical with embodiment 8, the conduction recording is vulcanized carboxy nitrile rubber/polypropylene thermoplastic elastomer entirely, and the results are shown in Table 2.
Comparative example 5
Except not adding carbon nanotube, other are identical with embodiment 8, and experimental result is listed in table 2.
Embodiment 10
Replace with full sulfuration butylbenzene powdered rubber (with embodiment 1) except entirely vulcanizing carboxyl butyronitrile powdered rubber, carbon nanotube becomes beyond 2/100 with the gross weight ratio of polypropylene and full sulfuration butylbenzene powdered rubber, all the other are all identical with embodiment 8, and the conduction recording is vulcanized styrene-butadiene rubber(SBR)/polypropylene thermoplastic elastomer entirely, and the results are shown in Table 2.
Comparative example 6
Except not adding carbon nanotube, other are identical with embodiment 10, and experimental result is listed in table 2.
Embodiment 11
Replace with full silicon sulfide powdered rubber (Beijing Chemical Research Institute of China Petrochemical Industry except entirely vulcanizing butylbenzene powdered rubber, VP601, gel content 81%wt, median size 150nm), all the other are all identical with embodiment 10, and the results are shown in Table 2 for the full sulphurated siliastic/polypropylene thermoplastic elastomer of conductivity type recording.
Comparative example 7
Except not adding carbon nanotube, other are identical with embodiment 11, and experimental result is listed in table 2.
Embodiment 12
Except polypropylene is replaced with to maleic anhydride inoculated polypropylene (Ningbo NengZhiGuang New Materials Science Co., Ltd, GPM200AL, percentage of grafting 0.8%wt), carbon nanotube becomes beyond 2/100 with the gross weight ratio of polypropylene and full sulfuration carboxyl butyronitrile powdered rubber, all the other are all identical with embodiment 8, and the conduction recording is vulcanized carboxyl butyronitrile/polypropylene thermoplastic elastomer entirely, and the results are shown in Table 2.
Embodiment 13
To entirely vulcanize Carboxy powdered rubber (Beijing Chemical Research Institute of China Petrochemical Industry, VP201A, gel content 87%wt, median size 150nm), carbon nanotube (with embodiment 1), nylon 6 (Ube, 1013B), antioxidant 1010 (Switzerland vapour Ba Jiaji production) and 168 (Switzerland vapour Ba Jiaji productions) fully mix in stirrer.The weight ratio of wherein entirely vulcanizing Carboxy powdered rubber and nylon 6 is 50/50, carbon nanotube is 4/100 with the gross weight ratio of nylon 6 and full sulfuration butylbenzene powdered rubber, and antioxidant 1010 and 168 is respectively 0.2% and 0.4% of powdered rubber and poly gross weight.Use afterwards Branbender torque rheometer melt blending, blend oil bath temperature and rheometer revolution are set as 240 ℃ and 60 rpms (rpm), when material plasticizing evenly after discharging.Gained sample, with two roller mills (temperature is made as 240 ℃) in flakes, is made standard batten by material by compression molding, carries out properties test, and the conductivity type recording vulcanizes carboxylic styrene-butadiene rubber/nylon 6 thermoplastic elastomers entirely, and the results are shown in Table 2.Accompanying drawing 1 is the TEM picture of reflection the present embodiment fully sulfurized thermoplastic elastomer Micro.Wherein black particle shape shade is full sulfuration Carboxy powdered rubber, and being distributed in intergranular pipe is carbon nanotube.
Comparative example 8
Except not adding carbon nanotube, other are identical with embodiment 13, and experimental result is listed in table 2.
Table 2
Claims (15)
1. a conduction fully sulfurized thermoplastic elastomer, comprises the following component of blend:
A. thermoplastics; B. there is the rubber particles of crosslinking structure; C. conductive filler material; The median size of the rubber particles of wherein said components b is 0.02-1 μ m, and gel content is 60% weight or higher; The conductive filler material of described amount of component b is carbon nanotube;
The Micro of described conduction fully sulfurized thermoplastic elastomer is: the thermoplastics of described component a is external phase, and the rubber particles of described components b is disperse phase, and the carbon nanotube dispersed of described amount of component b is in external phase and be distributed between rubber particles;
The weight ratio of the thermoplastics of the rubber particles of wherein said components b and component a is 30 ︰ 70～75 ︰ 25; The content of the conductive filler material of amount of component b is take the rubber particles of components b and the thermoplastics gross weight of component a as 100 parts, and its parts by weight are 0.5～10 part.
2. conduction fully sulfurized thermoplastic elastomer according to claim 1, is characterized in that the thermoplastics of described component a is selected from least one in following material: the graft modification thing of Ju Bing Xi ﹑ polyethylene, polymeric amide, polyvinyl chloride, urethane, polyester, polycarbonate, polyoxymethylene, polystyrene, polyphenylene sulfide, polyimide, polysulfones or above thermoplastics.
3. conduction fully sulfurized thermoplastic elastomer according to claim 1, the rubber particles with crosslinking structure that it is characterized in that described components b is equal phase structure.
4. conduction fully sulfurized thermoplastic elastomer according to claim 1, the gel content that it is characterized in that the rubber particles with crosslinking structure of described components b is 75% weight or higher.
5. conduction fully sulfurized thermoplastic elastomer according to claim 1, the median size that it is characterized in that the rubber particles with crosslinking structure of described components b is 0.05～0.5 μ m.
6. conduction fully sulfurized thermoplastic elastomer according to claim 1, is characterized in that described carbon nanotube is selected from least one in following material; Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes.
7. conduction fully sulfurized thermoplastic elastomer according to claim 6, is characterized in that described carbon nanotube is multi-walled carbon nano-tubes.
8. conduction fully sulfurized thermoplastic elastomer according to claim 1, the mean diameter that it is characterized in that described carbon nanotube is that 0.4～500nm, mean length are that 0.1～1000 μ m, length-to-diameter ratio are 0.25～2500000.
9. conduction fully sulfurized thermoplastic elastomer according to claim 8, the mean diameter that it is characterized in that described carbon nanotube is that 1～50nm, mean length are that 1～50 μ m, length-to-diameter ratio are 20～10000.
10. conduction fully sulfurized thermoplastic elastomer according to claim 1, the weight ratio that it is characterized in that the rubber particles of described components b and the thermoplastics of component a is 50 ︰ 50～75 ︰ 25.
11. conduction fully sulfurized thermoplastic elastomers according to claim 1, is characterized in that the content of conductive filler material of described amount of component b is take the rubber particles of components b and the thermoplastics gross weight of component a as 100 parts, and its parts by weight are 0.5～7 part.
12. according to the conduction fully sulfurized thermoplastic elastomer described in any one of claim 1～11, and the rubber particles with crosslinking structure that it is characterized in that described components b is fully vulcanized powder rubber or cross-linked powdered rubber.
13. conduction fully sulfurized thermoplastic elastomers according to claim 12, it is characterized in that described fully vulcanized powder rubber comprises at least one of following material: the right Xiang Jiao of form of finely divided powder, mehtod Tian ﹑ form of finely divided powder, mehtod Ding benzene Xiang Jiao ﹑ form of finely divided powder, mehtod carboxylic styrene-butadiene rubber, Vulcanized Powdered Nitrile Rubber, form of finely divided powder, mehtod carboxy nitrile rubber, form of finely divided powder, mehtod polybutadiene rubber, form of finely divided powder, mehtod chloroprene rubber, fully sulfurized silicon rubber powder, form of finely divided powder, mehtod acrylic elastomer, form of finely divided powder, mehtod vinylpyridiene-styrene-butadiene rubber, form of finely divided powder, mehtod polyisoprene rubber, form of finely divided powder, mehtod isoprene-isobutylene rubber, form of finely divided powder, mehtod thiorubber, form of finely divided powder, mehtod Acrylester Butadiene Rubber, form of finely divided powder, mehtod urethanes or form of finely divided powder, mehtod viton.
14. conduction fully sulfurized thermoplastic elastomers according to claim 12, is characterized in that described cross-linked powdered rubber comprises cross-linked powdery styrene-butadiene rubber(SBR) or cross-linked powdery polybutadiene rubber.
15. 1 kinds according to the preparation method of the conduction fully sulfurized thermoplastic elastomer described in any one of claim 1～14, it is characterized in that by the component including thermoplastics, the rubber particles with crosslinking structure of components b and the conductive filler material of amount of component b of described component a by plastic blend equipment a melt blending and make described conduction fully sulfurized thermoplastic elastomer.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110052093.9A CN102653613B (en) | 2011-03-04 | 2011-03-04 | Conductive fully-vulcanized thermoplastic elastomer and preparation method thereof |
| PCT/CN2012/071865 WO2012119526A1 (en) | 2011-03-04 | 2012-03-02 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
| JP2013555739A JP5771290B2 (en) | 2011-03-04 | 2012-03-02 | Conductive fully vulcanized thermoplastic elastomer and process for its production |
| ES12755604T ES2899158T3 (en) | 2011-03-04 | 2012-03-02 | Fully vulcanized electrically conductive thermoplastic elastomer and method of preparing same |
| EP12755604.1A EP2682431B1 (en) | 2011-03-04 | 2012-03-02 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
| KR1020137021006A KR20140050576A (en) | 2011-03-04 | 2012-03-02 | Electrically conductive, fully vulcanized, thermoplastic elastomer and preparation method thereof |
| US14/001,948 US9424959B2 (en) | 2011-03-04 | 2012-03-02 | Conductive full vulcanized thermoplastic elastomer and its preparation method |
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| CN104098813B (en) * | 2013-04-12 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of conductive plastics and preparation method thereof |
| CN104098834B (en) * | 2013-04-12 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of conducting polymer composite material and preparation method thereof |
| CN104098795B (en) * | 2013-04-12 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of conductive thermoplastic elastomer and preparation method thereof |
| CN103804911A (en) * | 2014-02-27 | 2014-05-21 | 苏州市涵信塑业有限公司 | Improved PSU (Polysulphone) plastic |
| CN103965642A (en) * | 2014-05-12 | 2014-08-06 | 四川大学 | Polyphenylene sulfide/silicone rubber thermoplastic elastomer as well as preparation method and application thereof |
| CN104031387B (en) * | 2014-06-27 | 2016-09-07 | 自贡中天胜新材料科技有限公司 | A kind of self-lubricating polyimides elastic wear-resisting composite and preparation method |
| CN105037832A (en) * | 2015-09-16 | 2015-11-11 | 合肥海畅电气技术有限公司 | Arc extinguishing shell material of motor protection controller |
| CN105968779A (en) * | 2016-07-06 | 2016-09-28 | 苏州科淼新材料有限公司 | Iron fiber nano rubber conductive material and preparation method thereof |
| CN107746565A (en) * | 2017-10-26 | 2018-03-02 | 吉林大学 | Thermoplastic polyurethane composite for slush molding and preparation method thereof |
| CN110819118B (en) * | 2018-08-14 | 2021-06-01 | 北京化工大学 | Conductive elastomer composite material for wearable device and preparation method thereof |
| CN112341681B (en) * | 2020-11-26 | 2022-02-11 | 中国石油大学(北京) | Rubber-plastic blending modified hydrogenated nitrile rubber and preparation method and application thereof |
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