CN101161726B - 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 PDFInfo
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- CN101161726B CN101161726B CN2007100773777A CN200710077377A CN101161726B CN 101161726 B CN101161726 B CN 101161726B CN 2007100773777 A CN2007100773777 A CN 2007100773777A CN 200710077377 A CN200710077377 A CN 200710077377A CN 101161726 B CN101161726 B CN 101161726B
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 57
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 238000012545 processing Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 239000007822 coupling agent Substances 0.000 claims description 27
- 239000002041 carbon nanotube Substances 0.000 claims description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- 239000004917 carbon fiber Substances 0.000 claims description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- -1 Polyphenylene Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
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- 238000011068 loading method Methods 0.000 claims description 3
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
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- 150000004645 aluminates Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 2
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 7
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- 239000011231 conductive filler Substances 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
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
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.
The diameter of described electro-conductive fiber is 10～200 μ m, is advisable with 20～100 μ m, and length-to-diameter ratio is 5～10000, is advisable with 20～5000; Described electro-conductive fiber comprises macrofiber or chopped strand, and wherein long stapled length is 10～150mm, is advisable with 50～100mm, and the length of chopped strand is 1～10mm, is advisable with 2～6mm; 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 45～1100m
2/ g, particle diameter are 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 8～50nm, and the carbon bore is 5～15nm, and the carbon length of tube is about 10～30 μ m.
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 200～450,265～290 ℃ 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 (7)
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%;
Described polyphenylene sulfide is a s-generation linear resin, and molecular weight is greater than 50000; Described conductive powder is that in superconduction graphite, superconduction carbon black, the carbon nanotube two or more are compound; Described superconduction graphite is the crystalline structure with no lattice defect, and the averageparticle crystalline substance of graphite particle is 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.
2. 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.
3. 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.
4. 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 with the mixed volume ratio of staple fibre: 1-8: 1.
5. 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.
6. 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.
7. 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 10-30min in the mixed aqueous solution of titanate coupling agent, dehydrated alcohol, treatment temp 30-70 ℃, make coupling agent fully react with fiber or powder surface, wherein three's proportioning is: the coupling agent of the electro-conductive fiber of 70-90% or conductive powder, 0.5-2.5%, the dehydrated alcohol of 10-20%;
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 200-450 rpm/min, processing temperature 265-290 ℃, residence time 2-3mi n, 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.
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