CN101161726A - Highly-conductive polyphenylene sulfide composite material and method for making same - Google Patents

Highly-conductive polyphenylene sulfide composite material and method for making same Download PDF

Info

Publication number
CN101161726A
CN101161726A CNA2007100773777A CN200710077377A CN101161726A CN 101161726 A CN101161726 A CN 101161726A CN A2007100773777 A CNA2007100773777 A CN A2007100773777A CN 200710077377 A CN200710077377 A CN 200710077377A CN 101161726 A CN101161726 A CN 101161726A
Authority
CN
China
Prior art keywords
conductive
polyphenylene sulfide
fiber
highly
electro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2007100773777A
Other languages
Chinese (zh)
Other versions
CN101161726B (en
Inventor
徐东
贺永
黄义宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Keju New Material Co Ltd
Original Assignee
Shenzhen Keju New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Keju New Material Co Ltd filed Critical Shenzhen Keju New Material Co Ltd
Priority to CN2007100773777A priority Critical patent/CN101161726B/en
Publication of CN101161726A publication Critical patent/CN101161726A/en
Application granted granted Critical
Publication of CN101161726B publication Critical patent/CN101161726B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a high electric conduction polyphenylene sulfide (PPS) composite material and the preparation method thereof. The percentage by weight of the compositions of the high electric conduction polyphenylene sulfide composite material is as follows: 40 to 70 percent of polyphenylene sulfide, 5 to 30 percent of conducting fiber, 5 to 30 percent of conducting powder, and other auxiliary agents from 0 to 5 percent. The conducting fiber and conducting powder in the conducing plastics provided by the invention disperse evenly with a plurality of lapping joints and high electric conductivity, thereby remarkably improving electric conductivity. The surface resistivity and volume resistivity of the material respectively reach 0.3-11.0 ohm and 0.07-8.5 ohm*cm, thereby meeting the requirements of plastic shaping techniques such as repeated injection molding, plastic extruding or die stamping. The processing art of the material is simple and can control the conducting fiber and conducting carbon black to evenly disperse in plastic particles, thereby enabling the PPS composite material to have high electric conductivity and meeting the requirements of industrial big production.

Description

Highly-conductive polyphenylene sulfide composite material and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of highly-conductive polyphenylene sulfide composite material and preparation method thereof.
Background technology
PPS is a kind of thermoplastic special engineering plastic of excellent combination property, and its outstanding feature is high temperature resistant, corrosion-resistant, radiation hardness, do not fire, mechanical property and electrical property excellence.Be mainly used in automobile making, electronic apparatus, mechanical industry, chemical industry instrument and space industry etc.But PPS is the same with other plastics, is its insulativity and dielectric properties with the key distinction of metal, and this has limited it can not replace metal in some field.Along with industrial production and science and technology development, having higher requirement to electro-conductive material in field such as field that some are had relatively high expectations to the material conductivity such as electro-engineering, electromagnetic shielding, electronic information, wishes that material has excellent comprehensive performances.
At present, the means that the preparation electro-conductive material is commonly used are respectively that machinery is compound, chemical doping and ion implantation etc., and the most frequently used be mechanical compound processing method.The machinery composite conducting material is meant conductive agent is filled into the electrical conductor that forms in the plastics in the mode of mechanical blending.Main at present research and the conductive agent of using have carbon system to comprise carbon black, graphite and carbon fiber; Metal comprises powder, thin slice, fiber, whisker, nano material of metal oxides such as iron, copper, silver etc.Carbon nanotube (CNTs) is a kind of novel material, by the tubular fiber that one or more layers carbon atom in the graphite curls and forms, has performances such as excellent mechanics, electricity, optics.CNTs itself have unique high conductivity (1000～2000S/cm), can be by big current density (106A/cm 2), have bigger length-to-diameter ratio again simultaneously, can greatly improve the conductivity of polymer composites with polymkeric substance is compound, thereby be well suited for doing conductive filler material.Carbon nanotube is with respect to other conductive filler materials, and consumption seldom just can form the conduction network chain, and its density is very little, is not easy the effect coagulation because of gravity.Be consistency and the dispersiveness of improving carbon nanotube, need carbon nanotube is carried out chemically modified, make its hydroxyl or carboxyl on the band of position, termination, thereby make the carbon nano tube surface activation.Existing research about the CNTs filled polymer mainly is confined to the preparation method, and is as solution method, in-situ polymerization, melt-blending process etc., still rare with the report of its preparation high-conductive plastic.
Domestic preparation and the application that has partial monopoly to report high-conductive plastic, reported that as patent CN1528817A preparation method, patent CN1583867 that a kind of polyolefine/carbon black PTC conducing composite material and preparation method thereof, patent CN1990535A have introduced a kind of conductive polypropylene material of excellent combination property disclose a kind of preparation method of antistatic and conducting polypropylene blend, but be based on polyolefinic performance own, can't use as structural material, the addition of conductive carbon black is too much simultaneously, has influenced performance of composites; In addition, utilize engineering plastics to prepare conductive plastics in addition for matrix, described the method that polymeric amide and polyphenylene oxide melt kneading prepare conductive plastics in detail as patent CN1906249, but the method for above-mentioned processing has shortcomings such as complex procedures, conductive plastics itself is not fire-retardant, heat-drawn wire is not ideal enough, thereby has limited the application of this type of conductive engineering plastics under severe condition such as high heat, high humidity, high strength.
Summary of the invention
The technical problem to be solved in the present invention is, at conductive plastics of the prior art in the selection of conductive filler material with obvious deficiency and the shortcoming formed, a kind of thermoplastic conductive plastics that comprised the three-dimensional network shape arrangement architecture that carbon nanotube constitutes by electro-conductive fiber and conductive powder that have are proposed, have that production process is simple, electro-conductive fiber be uniformly dispersed, conduct electricity controlled, plasticity-strong, the characteristics that can recycle repeatedly.
Another technical problem that the present invention will solve is, at conductive plastics of the prior art in the selection of matrix resin and obvious deficiency and the shortcoming on the complete processing, propose to select this special engineering plastics of polyphenylene sulfide as matrix resin, make the material that makes have outstanding electroconductibility and excellent physical and mechanical performance, satisfied this type of conductive engineering plastics and can be used as the application of structural material under severe condition such as high heat, high humidity, high strength.
For solving the problems of the technologies described above, the invention provides a kind of highly-conductive polyphenylene sulfide composite material, its composition is (%) by weight ratio: polyphenylene sulfide 40～70%, electro-conductive fiber 5～30%, conductive powder 5～30%, other auxiliary agents 0～5%, wherein said conductive filler material are uniformly dispersed in PPS, overlapped points is many, electroconductibility is strong, and the mechanical property of material is superior.Simultaneously, described high conduction PPS matrix material satisfies the requirement of plastics molding process such as injection moulding repeatedly, extrusion molding or mold pressing, and described complete processing is simple, satisfies the requirement of industrialized production.
Described polyphenylene sulfide is a s-generation high molecular weight linear resin, and molecular weight is greater than 50000.
Described electro-conductive fiber is that in carbon fiber, nickel-coated carbon fibers, the copper carbon fiber one or more are compound.
The diameter of described electro-conductive fiber is 10～200 μ m, and length-to-diameter ratio is 20～10000; Described electro-conductive fiber comprises macrofiber or chopped strand, and wherein long stapled length is 10～150mm, and the length of chopped strand is 1～10mm; When electro-conductive fiber comprised macrofiber and staple fibre, described macrofiber was 5: 1～8: 1 with the mixed volume ratio of staple fibre.
Described conductive powder is that in superconduction graphite, superconduction carbon black, the carbon nanotube two or more are compound.
Described superconduction graphite must have the crystalline structure of no lattice defect, and to guarantee the electroconductibility of graphite particle, the averageparticle crystalline substance of graphite particle should be below the 1.5 μ m; Described superconduction carbon black should be unbodied vesicular structure, and their surface-area is about 45～1100m 2/ g, particle diameter are about 0.05～3.0 μ m; Described carbon nanotube should be many wall constructions of chemical Vapor deposition process preparation, and the most suitable with hydroxylated carbon nanotube, their specific surface area should be 50m 2More than/the g, the carbon external diameter of pipe is about 8～50nm, and the carbon bore is about 5～15nm, and the carbon length of tube is about 10～30 μ m.
Described coupling agent be titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, siloxanes coupling agent one or more are compound, preferential titanate coupling agent.
Described other auxiliary agent is processing characteristics and the final use properties that is used to improve highly-conductive polyphenylene sulfide composite material, is a kind of or any several composition of oxidation inhibitor, softening agent, surface treatment agent, photostabilizer.
The preparation method of highly-conductive polyphenylene sulfide composite material comprises step:
Step 1: electro-conductive fiber or conductive powder are fully soaked into 10～30min in the mixed aqueous solution of titanate coupling agent, dehydrated alcohol, 30～70 ℃ of treatment temps, make coupling agent fully react with fiber or powder surface, wherein three's proportioning is: 70～90% electro-conductive fiber or conductive powder, 0.5～2.5% coupling agent, 10～20% dehydrated alcohol;
Step 2: take by weighing polyphenylene sulfide by weight ratio, put into to do in the super mixer with the conductive powder of handling well, other auxiliary agent and mix 3～5min;
Step 3: the loading hopper of mixed raw materials in the step 2 being put into twin screw extruder, electro-conductive fiber is added by the side spout, it is that 20～1000rpm/min, screw speed 200～450rpm/min, 265～290 ℃ of processing temperatures, the residence time 2～3min, pressure are 12～18MPa that control mixes the speed of stirring, through melt extruding into line, cooling, cut granulation then, form the conductive plastics particle.
Above technical scheme as can be seen, the present invention has following beneficial effect:
1: the present invention adopts superelevation conductive filler material p-poly-phenyl thioether matrix material to carry out filling-modified, electro-conductive fiber in the conductive plastics is uniformly dispersed, electroconductibility height, resistivity stable, and have that light weight, addition are few, characteristics such as easily compound, easy processing, Application Areas are extensive.
2: when the highly-conductive polyphenylene sulfide composite material that the present invention makes has high conduction performance, also have high rigidity, high-modulus, mechanical property such as high temperature resistant.
3: the preparation technology of the highly-conductive polyphenylene sulfide composite material that the present invention proposes is simple, and can satisfy the processing requirement of plastic shaping processing such as injection moulding, extrusion molding or mold pressing repeatedly, can be widely used in electronic product.Field such as communication device, safety precaution.
Embodiment
Below by specific embodiment the present invention is described in detail.
The invention provides a kind of highly-conductive polyphenylene sulfide composite material, its composition is (%) by weight ratio: polyphenylene sulfide 40～70%, electro-conductive fiber 5～30%, conductive powder 5～30%, other auxiliary agents 0～5%.
Described polyphenylene sulfide is a s-generation high molecular weight linear resin, and molecular weight is greater than 50000.
Described electro-conductive fiber is that in carbon fiber, nickel-coated carbon fibers, the copper carbon fiber one or more are compound.
When described electro-conductive fiber comprised macrofiber and staple fibre, described macrofiber was 5: 1～8: 1 with the mixed volume ratio of staple fibre.
Described conductive powder is that in superconduction graphite, superconduction carbon black, the carbon nanotube two or more are compound.
Described coupling agent be titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, siloxanes coupling agent one or more are compound, preferential titanate coupling agent.
Described other auxiliary agent is processing characteristics and the final use properties that is used to improve highly-conductive polyphenylene sulfide composite material, is a kind of or any several composition of oxidation inhibitor, softening agent, surface treatment agent, photostabilizer.
The preparation method of highly-conductive polyphenylene sulfide composite material comprises step:
Step 1: electro-conductive fiber or conductive powder are fully soaked into 10～30min in the mixed aqueous solution of titanate coupling agent, dehydrated alcohol, 30～70 ℃ of treatment temps, make coupling agent fully react with fiber or powder surface, wherein three's proportioning is: 70～90% electro-conductive fiber or conductive powder, 0.5～2.5% coupling agent, 10～20% dehydrated alcohol.
Step 2: take by weighing polyphenylene sulfide by weight ratio, put into to do in the super mixer with the conductive powder of handling well, other auxiliary agent and mix 3～5min;
Step 3: the loading hopper of mixed raw materials in the step 2 being put into twin screw extruder, electro-conductive fiber is added by the side spout, it is that 20～1000rpm/min, screw speed 200～450rpm/min, 265～290 ℃ of processing temperatures, the residence time 2～3min, pressure are 12～18MPa that control mixes the speed of stirring, through melt extruding into line, cooling, cut granulation then, form the conductive plastics particle.
Embodiment 1:
In the present embodiment 1, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 20% superconduction carbon black, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 2:
In the present embodiment 2, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 19% superconduction carbon black, 1% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 3:
In the present embodiment 3, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 18% superconduction carbon black, 2% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 4:
In the present embodiment 4, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 17% superconduction carbon black, 3% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 5:
In the present embodiment 5, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 12% superconduction carbon black, 4% superconduction graphite, 4% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 6:
In the present embodiment 6, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 10% superconduction carbon black, 6% superconduction graphite, 4% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Embodiment 7:
In the present embodiment 7, described high conduction PPS matrix material comprises the 59.0%PPS resin, 20% conduction chopped carbon fiber, 8% superconduction carbon black, 8% superconduction graphite, 4% carbon nanotube, 1% processing aid.Described chopped carbon fiber, the length of fiber are 6mm, and diameter is 20 μ m.With 2% coupling agent conductive powder is handled earlier, then the material that mixes is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material.Wherein, complete processing is as follows: twin screw extruder one district's temperature: 265 ℃; Two districts: 270 ℃; Three districts: 270 ℃; Four districts: 275 ℃; Five district's temperature: 275 ℃; Six districts: 275 ℃; Seven districts: 280 ℃; Eight districts: 280 ℃; Head: 265 ℃; The residence time 3～4min, pressure are 15MPa.
Performance test:
Prepared alloy material, its mechanical property is tested according to GB GB/T 1040; Its flexural strength and modulus in flexure are tested by GB GB 9341/T; Its notched Izod impact strength is tested by GB/T 1043; Its heat-drawn wire performance is tested according to GB 1634-79; Its vertical combustion is tested by GB GB/T2408-96; Its resistivity is tested according to ISO60093.
The prescription and the material property of embodiment 1～7, Comparative Examples see Table 1:
Table 1
Form Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Comparative Examples 7
PPS(％) 59.0 59.0 59.0 59.0 59.0 59.0 59.0
Electro-conductive fiber (%) 20.0 20.0 20.0 20.0 20.0 20.0 20.0
Conductive powder (%) The superconduction carbon black 20.0 19.0 18.0 17.0 12.0 10.0 8.0
Superconduction graphite 0 0 0 0 4.0 6.0 8.0
Carbon nanotube 0 1.0 2.0 3.0 4.0 4.0 4.0
Other auxiliary agent (%) 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Notched Izod impact strength (KJ/m 2) 8.5 9.0 10.5 11.0 11.5 10.5 10.5
Tensile strength (MPa) 140 145 158 163 165 157 152
Elongation at break (%) 1.0 0.9 1.0 1.2 1.1 0.9 1.4
Flexural strength (MPa) 155 175 185 205 210 186 175
Modulus in flexure (MPa) 12000 12500 14000 14500 14000 13500 13000
Surface resistivity (Ω) 2.2×10 3 285 40 11 1.3 0.3 3.8
Volume specific resistance (Ω cm) 1.3×10 3 120 23 8.5 0.65 0.07 1.5
By among the last table embodiment 1 as can be seen, electro-conductive fiber and conductive powder can obviously reduce the resistivity of PPS matrix material, but excessive carbon black adds in the conducing composite material, can cause the mechanical property such as tensile strength, flexural strength, notched Izod impact strength of PPS matrix material obviously to descend.According to this patent, can realize increasing substantially the conductivity of matrix material by adding a spot of carbon nanotube, improve the mechanical property of material simultaneously again.For example can find out from embodiment 2～6 that when the content of conductive powder maintained 20%, the resistivity of PPS matrix material reduced rapidly along with the adding of carbon nanotube; When especially content of carbon nanotubes is between 3～4%, the surface resistivity of polyphenyl thioether composite material and volume specific resistance can be reduced to 0.3～11.0 Ω and 0.07～8.5 Ω cm respectively, other performance of material all maintains higher numerical value as tensile strength, modulus in flexure, heat-drawn wire etc. simultaneously.Can find out from embodiment 5～7, interpolation superconduction graphite also reduces the resistivity of material effectively, superconduction carbon black and superconduction graphite mass ratio be positioned at 3: 1～and 1: 1 o'clock, best results, in embodiment 6, superconduction carbon black and superconduction graphite mass ratio are 5: 3 o'clock, and the surface resistivity of PPS matrix material and volume specific resistance are reduced to 0.3 Ω and 0.07 Ω cm respectively; If the further deal that improves superconduction graphite, the electroconductibility of material and mechanical property meeting decrease to some degree, so the superconduction carbon black is controlled in suggestion and superconduction graphite mass ratio is positioned at 3: 1～1: 1.
More than highly-conductive polyphenylene sulfide composite material provided by the present invention and preparation method thereof is described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.

Claims (10)

1. highly-conductive polyphenylene sulfide composite material is characterized in that: it is formed and is (%) by weight ratio:
Polyphenylene thioether PPS 40～70%;
Electro-conductive fiber 5～30%;
Conductive powder 5～30%;
Other auxiliary agent 0～5%.
2. highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that: described polyphenylene sulfide is a s-generation linear resin, and molecular weight is greater than 50000.
3. highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that: described electro-conductive fiber is that in carbon fiber, nickel-coated carbon fibers, the copper carbon fiber one or more are compound.
4. highly-conductive polyphenylene sulfide composite material according to claim 3 is characterized in that: the diameter of described electro-conductive fiber is 10～200 μ m, and length-to-diameter ratio is 20～10000 μ m; Described electro-conductive fiber comprises macrofiber or chopped strand, and wherein long stapled length is 10～150mm, and the length of chopped strand is 1～10mm.
5. highly-conductive polyphenylene sulfide composite material according to claim 4 is characterized in that: when described electro-conductive fiber comprised macrofiber and staple fibre, described macrofiber was 5: 1～8: 1 with the mixed volume ratio of staple fibre.
6. highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that: described conductive powder is that in superconduction graphite, superconduction carbon black, the carbon nanotube two or more are compound.
7. highly-conductive polyphenylene sulfide composite material according to claim 6 is characterized in that: described superconduction graphite is the crystalline structure with no lattice defect, and the averageparticle crystalline substance of graphite particle should be below the 1.5 μ m; Described superconduction carbon black is unbodied vesicular structure, and its surface-area is 45～1100m 2/ g, particle diameter are about 0.05～3.0 μ m; Described carbon nanotube is many wall constructions of chemical Vapor deposition process preparation, and its surface-area is 50m 2More than/the g, the carbon external diameter of pipe is 8～50nm, and the carbon bore is about 5～15nm, and the carbon length of tube is 10～30 μ m.
8. highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that: described coupling agent is that one or more are compound for titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, siloxanes coupling agent.
9. highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that: described other auxiliary agent is a kind of or any several composition of oxidation inhibitor, softening agent, surface treatment agent, photostabilizer.
10. the preparation method of highly-conductive polyphenylene sulfide composite material according to claim 1 is characterized in that, comprises step:
Step 1: electro-conductive fiber or conductive powder are fully soaked into 10～30 min in the mixed aqueous solution of titanate coupling agent, dehydrated alcohol, 30～70 ℃ of treatment temps, make coupling agent fully react with fiber or powder surface, wherein three's proportioning is: 70～90% electro-conductive fiber or conductive powder, 0.5～2.5% coupling agent, 10～20% dehydrated alcohol;
Step 2: take by weighing polyphenylene sulfide by weight ratio, put into to do in the super mixer with the conductive powder of handling well, other auxiliary agent and mix 3～5min;
Step 3: the loading hopper of mixed raw materials in the step 2 being put into twin screw extruder, electro-conductive fiber is added by the side spout, it is that 20～1000rpm/min, screw speed 200～450rpm/min, 265～290 ℃ of processing temperatures, the residence time 2～3min, pressure are 12～18MPa that control mixes the speed of stirring, through melt extruding into line, cooling, cut granulation then, form the conductive plastics particle.
CN2007100773777A 2007-09-28 2007-09-28 Highly-conductive polyphenylene sulfide composite material and method for making same Expired - Fee Related CN101161726B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007100773777A CN101161726B (en) 2007-09-28 2007-09-28 Highly-conductive polyphenylene sulfide composite material and method for making same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007100773777A CN101161726B (en) 2007-09-28 2007-09-28 Highly-conductive polyphenylene sulfide composite material and method for making same

Publications (2)

Publication Number Publication Date
CN101161726A true CN101161726A (en) 2008-04-16
CN101161726B CN101161726B (en) 2010-10-13

Family

ID=39296718

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007100773777A Expired - Fee Related CN101161726B (en) 2007-09-28 2007-09-28 Highly-conductive polyphenylene sulfide composite material and method for making same

Country Status (1)

Country Link
CN (1) CN101161726B (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101974222A (en) * 2010-10-21 2011-02-16 深圳市华力兴工程塑料有限公司 Process for preparing copper fiber modified conductive engineering plastic
CN102315509A (en) * 2010-06-29 2012-01-11 深圳富泰宏精密工业有限公司 Electronic device shell and manufacturing method thereof
CN102348297A (en) * 2011-10-19 2012-02-08 信阳市环宇针织服装有限公司 Nano carbon-fiber composite electrical heating material and preparing method thereof
CN102821563A (en) * 2011-06-10 2012-12-12 深圳富泰宏精密工业有限公司 Electronic device shell and manufacturing method thereof
CN102898834A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced electrically and thermally conductive polyphenylene sulfide composite material and preparation method thereof
CN102898835A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced thermal insulation polyphenylene sulfide composite material and preparation method thereof
CN103408935A (en) * 2013-07-25 2013-11-27 吴江龙硕金属制品有限公司 Antistatic plastic and preparation method thereof
CN103965632A (en) * 2014-04-23 2014-08-06 安徽依采妮纤维材料科技有限公司 Expanded graphite modified polyphenyl thioether material for car plastic parts
CN104927292A (en) * 2015-07-13 2015-09-23 苏州新区华士达工程塑胶有限公司 Conductive engineering plastic
CN104987659A (en) * 2015-08-10 2015-10-21 广州索润环保科技有限公司 Heat-resistant antistatic conductive polymer composite material and preparation method therefor and application thereof
CN106928708A (en) * 2015-12-30 2017-07-07 上海杰事杰新材料(集团)股份有限公司 A kind of lightweight electromagnetic shielding polyphenyl thioether material and preparation method thereof
CN107099138A (en) * 2017-05-12 2017-08-29 昆山茂高塑胶科技有限公司 A kind of carbon fiber modifying enhancing PPS automobile engine oil drain pan PP Pipe Compounds and its process
CN107163548A (en) * 2017-06-06 2017-09-15 深圳创怡兴实业有限公司 conductive flocking roller and preparation method thereof
CN108587166A (en) * 2018-04-16 2018-09-28 张家港大塚化学有限公司 High intensity heat conduction antistatic polyphenyl thioether composite material and preparation method thereof
CN108727819A (en) * 2017-04-13 2018-11-02 青岛创合新材料有限公司 A kind of fibre reinforced polyphenylene sulfide nanocomposite and preparation method and Novel radiating pipe application
CN108822545A (en) * 2018-06-14 2018-11-16 池州市骏智机电科技有限公司 A kind of conductive polyphenylene sulfide resin, preparation method and power battery
CN109553962A (en) * 2017-09-25 2019-04-02 现代自动车株式会社 For shielding the thermoplastic composite resin combination of electromagnetic wave
CN110014610A (en) * 2017-12-29 2019-07-16 胡哲久 A kind of PPS pipe and its production method and the machine used with combination production method
WO2021093303A1 (en) * 2019-11-14 2021-05-20 安徽旭升新材料有限公司 Carbon fiber composite material and preparation method therefor
CN113025040A (en) * 2021-03-09 2021-06-25 上海普利特伴泰材料科技有限公司 PPS (polyphenylene sulfide) special plastic capable of being used for conductive columns in lithium battery cover plate assembly
EP3714003A4 (en) * 2017-11-20 2021-08-04 Ticona LLC Fiber-reinforced polymer composition for use in an electronic module
US11129312B2 (en) 2017-11-20 2021-09-21 Ticona Llc Electronic module for use in an automotive vehicle

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8884826B2 (en) 2010-06-29 2014-11-11 Shenzhen Futaihong Precision Industry Co., Ltd. Housing of portable electronic device and method for making the same
CN102315509A (en) * 2010-06-29 2012-01-11 深圳富泰宏精密工业有限公司 Electronic device shell and manufacturing method thereof
CN102315509B (en) * 2010-06-29 2015-07-15 赛恩倍吉科技顾问（深圳）有限公司 Electronic device shell and manufacturing method thereof
CN101974222B (en) * 2010-10-21 2013-07-24 深圳市华力兴工程塑料有限公司 Process for preparing copper fiber modified conductive engineering plastic
CN101974222A (en) * 2010-10-21 2011-02-16 深圳市华力兴工程塑料有限公司 Process for preparing copper fiber modified conductive engineering plastic
CN102821563A (en) * 2011-06-10 2012-12-12 深圳富泰宏精密工业有限公司 Electronic device shell and manufacturing method thereof
CN102898834A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced electrically and thermally conductive polyphenylene sulfide composite material and preparation method thereof
CN102898835A (en) * 2011-07-28 2013-01-30 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced thermal insulation polyphenylene sulfide composite material and preparation method thereof
CN102898834B (en) * 2011-07-28 2015-12-16 合肥杰事杰新材料股份有限公司 Long carbon fiber strengthens current-conducting heat-conducting polyphenyl thioether matrix material and preparation method thereof
CN102898835B (en) * 2011-07-28 2016-01-20 合肥杰事杰新材料股份有限公司 Long glass fiber reinforced electric-insulating heat-conducting polyphenyl thioether composite material and preparation method thereof
CN102348297A (en) * 2011-10-19 2012-02-08 信阳市环宇针织服装有限公司 Nano carbon-fiber composite electrical heating material and preparing method thereof
CN103408935A (en) * 2013-07-25 2013-11-27 吴江龙硕金属制品有限公司 Antistatic plastic and preparation method thereof
CN103965632A (en) * 2014-04-23 2014-08-06 安徽依采妮纤维材料科技有限公司 Expanded graphite modified polyphenyl thioether material for car plastic parts
CN104927292A (en) * 2015-07-13 2015-09-23 苏州新区华士达工程塑胶有限公司 Conductive engineering plastic
CN104987659A (en) * 2015-08-10 2015-10-21 广州索润环保科技有限公司 Heat-resistant antistatic conductive polymer composite material and preparation method therefor and application thereof
CN106928708A (en) * 2015-12-30 2017-07-07 上海杰事杰新材料(集团)股份有限公司 A kind of lightweight electromagnetic shielding polyphenyl thioether material and preparation method thereof
CN108727819A (en) * 2017-04-13 2018-11-02 青岛创合新材料有限公司 A kind of fibre reinforced polyphenylene sulfide nanocomposite and preparation method and Novel radiating pipe application
CN107099138A (en) * 2017-05-12 2017-08-29 昆山茂高塑胶科技有限公司 A kind of carbon fiber modifying enhancing PPS automobile engine oil drain pan PP Pipe Compounds and its process
CN107163548A (en) * 2017-06-06 2017-09-15 深圳创怡兴实业有限公司 conductive flocking roller and preparation method thereof
CN109553962A (en) * 2017-09-25 2019-04-02 现代自动车株式会社 For shielding the thermoplastic composite resin combination of electromagnetic wave
CN109553962B (en) * 2017-09-25 2022-04-29 现代自动车株式会社 Thermoplastic composite resin composition for shielding electromagnetic wave
US11129312B2 (en) 2017-11-20 2021-09-21 Ticona Llc Electronic module for use in an automotive vehicle
EP3714003A4 (en) * 2017-11-20 2021-08-04 Ticona LLC Fiber-reinforced polymer composition for use in an electronic module
CN110014610A (en) * 2017-12-29 2019-07-16 胡哲久 A kind of PPS pipe and its production method and the machine used with combination production method
CN108587166A (en) * 2018-04-16 2018-09-28 张家港大塚化学有限公司 High intensity heat conduction antistatic polyphenyl thioether composite material and preparation method thereof
CN108822545A (en) * 2018-06-14 2018-11-16 池州市骏智机电科技有限公司 A kind of conductive polyphenylene sulfide resin, preparation method and power battery
WO2021093303A1 (en) * 2019-11-14 2021-05-20 安徽旭升新材料有限公司 Carbon fiber composite material and preparation method therefor
CN113025040A (en) * 2021-03-09 2021-06-25 上海普利特伴泰材料科技有限公司 PPS (polyphenylene sulfide) special plastic capable of being used for conductive columns in lithium battery cover plate assembly

Also Published As

Publication number Publication date
CN101161726B (en) 2010-10-13

Similar Documents

Publication Publication Date Title
CN101161726B (en) Highly-conductive polyphenylene sulfide composite material and method for making same
CN102585348B (en) Toughened conducting material and preparation method for toughened conducting material
CN1966564A (en) Reinforced toughening anti-aging polypropylene/nano calcium carbonate composite material and its preparation method
CN102558917B (en) Wrapped conducting nano material, conducting nano composite material and preparation method for wrapped conducting nano material and conducting nano composite material
CN102344654B (en) Hydrolysis resistant PET composite material and preparation method thereof
KR102347760B1 (en) Thermoplastic resin composite composition for shielding electromagnetc wave
CN103013075B (en) PET composite material, its preparation method and application
CN102898834A (en) Long glass fiber reinforced electrically and thermally conductive polyphenylene sulfide composite material and preparation method thereof
CN102746623A (en) Preparation method for insulating heat conduction material
CN102936372B (en) Polypropylene composite material, its preparation method and application
CN110564035A (en) Ultrahigh molecular weight polyethylene composite material and preparation method thereof
KR101309738B1 (en) Polymer/conductive filler composite with high electrical conductivity and the preparation method thereof
CN102234401A (en) Calcium sulfate whisker modified polystyrene composite material, and preparation method thereof.
CN102627830A (en) ABS / attapulgite composite material and preparation method thereof
KR101338199B1 (en) Polymer-conductive fillers composites and a preparing method thereof
CN101525478A (en) Polytrimethylene terephthalate/Poly-butylene terephthalate alloy material and preparation method thereof
CN108587166A (en) High intensity heat conduction antistatic polyphenyl thioether composite material and preparation method thereof
CN104672772A (en) Carbon fiber reinforced polyformaldehyde composite material with excellent conductivity and preparation method thereof
KR102125262B1 (en) Thermoplastic resin composition having excellent heat resistance and electromagnetic wave shielding property, method for preparing the same and injection-molded article prepared therefrom
CN105385118A (en) High-CTI-value flame-retardant and reinforced PBT (polybutylene terephthalate) composite material
KR101189563B1 (en) Polymer/hybridized conductive filler composite for automotive with high electromagnetic interference shielding efficiency and fabrication method for thereof
CN109749354A (en) A kind of polyether-ether-ketone composite wood and preparation method thereof
CN102898835A (en) Long glass fiber reinforced thermal insulation polyphenylene sulfide composite material and preparation method thereof
CN111048230B (en) Polymer conductive material and preparation method thereof
KR102084641B1 (en) An electrically conductive resin composition and a method for preparing the same

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Highly-conductive polyphenylene sulfide composite material and method for making same

Effective date of registration: 20150817

Granted publication date: 20101013

Pledgee: China Everbright Bank Shenzhen branch

Pledgor: Shenzhen Keju New Material Co., Ltd.

Registration number: 2015990000679

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20161202

Granted publication date: 20101013

Pledgee: China Everbright Bank Shenzhen branch

Pledgor: Shenzhen Keju New Material Co., Ltd.

Registration number: 2015990000679

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Highly-conductive polyphenylene sulfide composite material and method for making same

Effective date of registration: 20170106

Granted publication date: 20101013

Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch

Pledgor: Anhui science and Technology Co., Ltd.|Shenzhen branch poly new materials Co., Ltd.|Xu Dong

Registration number: 2016990001133

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20180904

Granted publication date: 20101013

Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch

Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd.|Xu Dong

Registration number: 2016990001133

PC01 Cancellation of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Highly-conductive polyphenylene sulfide composite material and method for making same

Effective date of registration: 20180912

Granted publication date: 20101013

Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch

Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd.

Registration number: 2018440020055

PE01 Entry into force of the registration of the contract for pledge of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20101013

Termination date: 20180928

CF01 Termination of patent right due to non-payment of annual fee