CN102675738B - Heat-resistant conductive polypropylene composite material and preparation method thereof - Google Patents
Heat-resistant conductive polypropylene composite material and preparation method thereof Download PDFInfo
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- CN102675738B CN102675738B CN201210148776.9A CN201210148776A CN102675738B CN 102675738 B CN102675738 B CN 102675738B CN 201210148776 A CN201210148776 A CN 201210148776A CN 102675738 B CN102675738 B CN 102675738B
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Abstract
The invention discloses a heat-resistant conductive polypropylene composite material and a preparation method thereof; the heat-resistant conductive polypropylene composite material comprises components in parts by mass: 45-75 parts of polypropylene, 5-30 parts of glass fiber and 16-24 parts of conductive carbon black. The composite material takes polypropylene as matrix resin and is prepared by a one-step melt kneading method; the glass fiber and the conductive carbon black have an obvious conductive synergistic effect, so that the composite material has excellent rigidity, heat resistance and good electrical conductivity; and the surface resistance is not higher than 109W, so that the composite material can be applied to a package and a chip carrier with anti-static requirement as well as a motor vehicle and the information and communication industry with electromagnetic shielding requirement.
Description
Technical field
The present invention relates to a kind of polypropylene composite material, particularly a kind of heat-resisting conductive polypropylene composite material and preparation method thereof.
Background technology
Fiber glass reinforced polypropylene is in original polypropylene matrix, adds glass fibre and other auxiliary agents, to improve rigidity and the thermotolerance of material, reduces shrinking percentage.In general, most of glass fiber reinforced materials is multiplex on the structural parts of product, is a kind of Structural Engineering material, has expanded the use range of acrylic resin.
Carbon black is the most frequently used conductive filler material, and raw material is easy to get, light weight, and its volume specific resistance is about 0.1Wcm, different according to loading level, resistivity that can flexible matrix material.Carbon black filled composite material forming processing is simple, has been widely used in the fields such as electronics, the energy, chemical industry, aerospace.
Patent CN200810217526.X discloses a kind of conductive plastics, and it comprises the polymeric substrate of 0-70%, the glass fibre of 15-50%, the conductive carbon black of 10-35%, and the properties-correcting agent of 1-5%.What this patent polymeric substrate adopted is polyphenylene oxide, it is mainly the thermotolerance that has improved conductive plastics, its preparation method completes in two steps, first glass fibre and matrix and graphitized carbon black and matrix are melt extruded respectively to granulation, and then two kinds of particles making are mixed according to certain ratio, must there is the strongthener of anti-static function.But, compare the disposable machine-shaping of extruding, many and loaded down with trivial details with two-step approach production stage, this patent is not done clear and definite elaboration to the electroconductibility of resulting materials after two kinds of mix particles simultaneously.
Patent CN200410024686.4 discloses a kind of preparation method of antistatic and conducting polypropylene (PP) blend, is by polypropylene, epoxy resin, after the glass fibre of coupling agent treatment and graphitized carbon black mix, join in Banbury mixer melt blending simultaneously and get final product.This method is relied on the polarity of epoxy resin, forms epoxy and is coated on fiberglass surfacing, and the structure of graphitized carbon black precedence partition this uniqueness in epoxy resin, has reduced the volume resistance of PP effectively.But exist, polypropylene and epoxy resin compatibility are poor, compound system mechanical property is not good, conduct electricity the defects such as synergistic effect reduction when simultaneously glass fiber content is higher.
Summary of the invention
For the shortcoming that overcomes prior art is with not enough, primary and foremost purpose of the present invention is to provide a kind of heat-resisting conductive polypropylene composite material with excellent rigidity, thermotolerance and good electroconductibility.
Another object of the present invention is to provide the preparation method of above-mentioned heat-resisting conductive polypropylene composite material.
The present invention is achieved by the following technical solutions:
A heat-resisting conductive polypropylene composite material, is characterized in that, comprises following component:
(A) polypropylene of 45 to 75 mass parts;
(B) glass fibre of 5 to 30 mass parts;
(C) graphitized carbon black of 16 to 24 mass parts.
Described polypropylene is selected from homo-polypropylene or Co-polypropylene, is preferably melting index at 20-80g/10min(230 ℃, homo-polypropylene 2.16kg).The present invention adopts the high molten polypropylene referring to, effective to glass fibre and graphitized carbon black moistened surface, impels two kinds of fillers to be mixed to get in forcing machine more even, guarantees still moulding smoothly when the more viscosity of filler is higher simultaneously.Meanwhile, the high molten homo-polypropylene molecular chain referring to is shorter, and crystal property is good, carbon black can be discharged outside lattice, and non-crystalline region content of carbon black is increased, and electroconductibility improves.
Described glass fibre is that diameter is the alkali free glass fibre of 7-18 μ m, can be alkali free glass fibre direct roving, can be also alkali free glass fibre chopped strand.
The DBP absorption value of described graphitized carbon black is at 100-460ml/100g.
Heat-resisting conductive polypropylene composite material of the present invention, can also comprise the compatilizer of (D) 0 to 5 mass parts and the oxidation inhibitor of 0.01 to 2 mass parts.
Compatilizer can improve the binding property between glass fibre and acrylic resin, improves rigidity or the toughness of matrix material.Compatilizer of the present invention is maleic anhydride grafts, is selected from one or more the mixture in maleic anhydride graft PE, maleic anhydride graft PP, maleic anhydride graft POE, maleic anhydride graft SEBS, maleic anhydride grafted ethene-propylene copolymer.
Described oxidation inhibitor is selected from one or more the mixture in Hinered phenols, hindered amines, phosphite ester kind antioxidant.
The surface resistivity of heat-resisting conductive polypropylene composite material of the present invention is not higher than 10
9Ω.
The preparation method of heat-resisting conductive polypropylene composite material of the present invention, comprises the steps:
A, the polypropylene that takes (A) 45 to 75 mass parts, the compatilizer of (D) 0 to 5 mass parts and the oxidation inhibitor of 0.01 to 2 mass parts add high-speed stirring mixer to mix, the material that obtains mixing;
B, the above-mentioned material mixing is added from the main spout of twin screw extruder, the graphitized carbon black of the glass fibre of (B) 5 to 30 mass parts, (C) 16 to 24 mass parts is added from two side spouts of twin screw extruder respectively, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing to obtain heat-resisting conductive polypropylene composite material.
The present invention compared with prior art, has following beneficial effect:
Heat-resisting conductive polypropylene composite material of the present invention is to take polypropylene as matrix resin, by a step melt kneading method, disposablely in twin screw extruder, completes the preparation that glass strengthens carbon black filled conducing composite material, and preparation technology is simple; Select the high molten acrylic resin referring to, when melt-processed, can make glass and graphitized carbon black mix, improve processibility, improve conductive effect simultaneously; Adding of glass fibre impels the surface resistivity of matrix material obviously to reduce, and conductive network can form when lower carbon black addition, and glass fibre and graphitized carbon black have obvious conduction synergistic effect; This heat-resisting conducing composite material has excellent rigidity, thermotolerance and good electroconductibility, and surface resistivity is not higher than 10
9w all can apply in having packing, the chip carrier of anti-electrostatic requirement and having Motor vehicles that electromagnetic shielding requires, information communication industry.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
In table 1, table 3 illustrated embodiment and comparative example formula: selected polypropylene is the PP HJ4045 that Korea S oiling company produces; Compatilizer is the maleic anhydride inoculated polypropylene PC-1 that Guangzhou Bai Chen company produces, and percentage of grafting is 0.5%; Carbon black is Cabot graphitized carbon black VXC-500; Glass fibre is the alkali-free short glass fiber ESC13-4.5-508A that Jushi Group Co., Ltd. produces; Oxidation inhibitor is the hindered phenol antioxygen Irganox 1010 of vapour Bagong department production and the compound of organophosphite Irganox 168, and ratio is 1:2.
Its preparation method: count by weight, take polypropylene, oxidation inhibitor and lubricant mixes the main spout at twin screw extruder after 10 minutes and adds in high-speed stirring mixer, glass fibre and graphitized carbon black add from two side spouts of forcing machine respectively, by regulating the main feeding capacity of feeding with side of feeding, control graphitized carbon black additional proportion, barrel temperature is controlled at 160-220 ℃, screw speed is 320 revs/min, melt extrudes granulation and get final product.
Performance test sample preparation:
The above-mentioned particle of extruding after dry 4 hours, is injection molded into standard model by injection moulding machine at 90 ℃, stretches, crooked, density and heat-drawn wire press iso standard and test, surface resistivity is lower than 10
4during W, adopt the test of digital multimeter ohms range, surface resistivity is higher than 10
4during W, adopt the examination of portable resistor instrumentation.Test result is in Table 2 and table 4.
Table 1: the formula of embodiment 1-7 forms
Table 2: the quantitative measurement result of embodiment 1-7
The formula of table 3: comparative example 1-4 forms
The quantitative measurement result of table 4: comparative example 1-4
In comparative example, for polypropylene/graphitized carbon black compound system, content of carbon black forms conducting network between 18-20 part, and surface resistivity arrives conduction rank.In an embodiment, for polypropylene/graphitized carbon black/glass fiber composite system, while adding 10 parts of glasses, content of carbon black forms conducting network between 16-18 part; Add 20 parts of glasses, content of carbon black has formed and has stablized conducting network in the time of 16 parts.Meanwhile, under identical content of carbon black, in system, add the fiberglass surfacing resistance several times of even several orders of magnitude that will decline.This explanation: (a) carbon black addition is lower can not form conducting network time, glass add the formation that can promote carbon black conducting network; (b) carbon black addition is higher while having formed conducting network, and adding of glass can be improved carbon black conducting network structure, has significantly collaborative electric action with carbon black.
Aspect mechanical property and thermal characteristics, glass fibre is the major cause of raising system rigidity and heat-drawn wire, and glass fiber content is higher, and amplitude is more obvious.
In sum, the raising that has added not only very big degree of glass fibre rigidity and the heat-drawn wire of matrix material, widened the Application Areas of material, can impel system conducting network to form when content of carbon black is lower, there is obvious conduction synergistic effect with graphitized carbon black simultaneously.
Claims (7)
1. a heat-resisting conductive polypropylene composite material, is characterized in that, comprises following component:
(A) polypropylene of 45 to 75 mass parts;
(B) glass fibre of 5 to 30 mass parts;
(C) graphitized carbon black of 16 to 24 mass parts;
Also comprise the compatilizer of (D) 0 to 5 mass parts and the oxidation inhibitor of 0.01 to 2 mass parts;
Described polypropylene is at 230 ℃, and under 2.16kg condition, melting index is in the homo-polypropylene of 20-80g/10min;
Its preparation method comprises the steps:
A, the polypropylene that takes (A) 45 to 75 mass parts, the compatilizer of (D) 0 to 5 mass parts and the oxidation inhibitor of 0.01 to 2 mass parts add high-speed stirring mixer to mix, the material that obtains mixing;
B, the above-mentioned material mixing is added from the main spout of twin screw extruder, the graphitized carbon black of the glass fibre of (B) 5 to 30 mass parts, (C) 16 to 24 mass parts is added from two side spouts of twin screw extruder respectively, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing to obtain heat-resisting conductive polypropylene composite material.
2. heat-resisting conductive polypropylene composite material according to claim 1, is characterized in that, described glass fibre is that diameter is the alkali free glass fibre of 7-18 μ m.
3. heat-resisting conductive polypropylene composite material according to claim 1, is characterized in that, the DBP absorption value of described graphitized carbon black is 100-460ml/100g.
4. heat-resisting conductive polypropylene composite material according to claim 1, it is characterized in that, described compatilizer is maleic anhydride grafts, is selected from one or more the mixture in maleic anhydride graft PE, maleic anhydride graft PP, maleic anhydride graft POE, maleic anhydride graft SEBS, maleic anhydride grafted ethene-propylene copolymer.
5. heat-resisting conductive polypropylene composite material according to claim 1, is characterized in that, described oxidation inhibitor is selected from one or more the mixture in Hinered phenols, hindered amines, phosphite ester kind antioxidant.
6. heat-resisting conductive polypropylene composite material according to claim 1, is characterized in that, described heat-resisting conductive polypropylene composite material surface resistivity is not higher than 10
9Ω.
7. the preparation method of the heat-resisting conductive polypropylene composite material described in claim 1 ~ 6 any one, is characterized in that, comprises the steps:
A, the polypropylene that takes (A) 45 to 75 mass parts, the compatilizer of (D) 0 to 5 mass parts and the oxidation inhibitor of 0.01 to 2 mass parts add high-speed stirring mixer to mix, the material that obtains mixing;
B, the above-mentioned material mixing is added from the main spout of twin screw extruder, the graphitized carbon black of the glass fibre of (B) 5 to 30 mass parts, (C) 16 to 24 mass parts is added from two side spouts of twin screw extruder respectively, through overmulling refining ﹑, squeeze out ﹑ and draw the cold but ﹑ of bar ﹑ pelletizing to obtain heat-resisting conductive polypropylene composite material.
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| CN107698870A (en) * | 2017-10-27 | 2018-02-16 | 夏杰 | A kind of polypropene composition and preparation method thereof |
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| CN103540051A (en) * | 2013-08-22 | 2014-01-29 | 吴江龙硕金属制品有限公司 | Electroconductive plastic |
| CN103450563A (en) * | 2013-08-23 | 2013-12-18 | 吴江龙硕金属制品有限公司 | Conductive toughened plastic |
| CN103971775A (en) * | 2014-05-09 | 2014-08-06 | 北京化工大学 | High temperature resistance neutron shield material and preparation method thereof |
| CN104045913A (en) * | 2014-07-10 | 2014-09-17 | 苏州新区华士达工程塑胶有限公司 | Conductive polypropylene |
| CN104260468B (en) * | 2014-09-17 | 2016-08-24 | 苏州凯丰电子电器有限公司 | A kind of conductive plastic plate and preparation method thereof |
| CN105482247A (en) * | 2015-12-04 | 2016-04-13 | 福建海源新材料科技有限公司 | Glass fiber and polypropylene battery case with conductive performance, and making method thereof |
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| CN108192207A (en) * | 2017-12-28 | 2018-06-22 | 聚威工程塑料(上海)有限公司 | A kind of high-performance conductive PP composite material and preparation method |
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| CN110591230A (en) * | 2019-10-15 | 2019-12-20 | 安徽强茗塑业科技有限公司 | Fiber-reinforced PP material and preparation method thereof |
| CN113881146A (en) * | 2021-09-18 | 2022-01-04 | 金发科技股份有限公司 | Wear-resistant high-impact polypropylene composition and preparation method and application thereof |
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| CN101260207B (en) * | 2008-03-20 | 2011-05-25 | 苏州大学 | Antistatic polyolefin material with low content of carbon black and preparation method thereof |
| CN101402776B (en) * | 2008-11-04 | 2010-12-01 | 惠州市沃特新材料有限公司 | Electroconductive plastics and method of producing the same |
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