CN102532882B - Conductive nylon plastic and preparation method thereof - Google Patents
Conductive nylon plastic and preparation method thereof Download PDFInfo
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- CN102532882B CN102532882B CN201210002707.7A CN201210002707A CN102532882B CN 102532882 B CN102532882 B CN 102532882B CN 201210002707 A CN201210002707 A CN 201210002707A CN 102532882 B CN102532882 B CN 102532882B
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Abstract
The invention relates to conductive nylon plastic. The conductive nylon plastic comprises 65 to 90 percent of polymer carrier, 5 to 30 percent of conductive carbon black and 0.05 to 3 percent of modifier. A preparation method for the conductive nylon plastic comprises the following steps: preparing the materials according to the formula; mixing and forming by using a banbury mixer; and pelleting by using a double-screw extruder to prepare the conductive nylon plastic. Compared with the prior art, the conductive nylon plastic can be directly used without any processing acid, so the intermediate production link and production equipment can be reduced; the conductive nylon plastic is high in processing flowability and stable in production; conductivity is excellent and the conductive nylon plastic with the resistivity of 105 ohm . cm and below105 ohm . cm can be produced; mechanical and physical properties are excellent; and the product is manufactured by a banbury mixer and the double-screw extruder, so the production environment and the ambient environment are not polluted.
Description
Technical field
The present invention relates to the conductive plastics field, concrete, the present invention relates to conductive nylon plastic and preparation method thereof.
Background technology
Conductive plastics is that resin and conducting material are mixed, the functional macromolecule material of being processed with the processing mode of plastics.Press the making method classification of conductive plastics, can be divided into structural conductive plastics and composite conductive plastic.The structural conductive plastics claim again the intrinsically conducting plastics, refer to the plastics that itself have electroconductibility or have electroconductibility after chemical modification.The production cost of this family macromolecule material is high, technology difficulty is large, so far there is no a large amount of production, the conducting polymer composite of widespread use now is all generally the composite polymer material, and its filler mainly contains: metal dispersed system, carbon black system, organic complex dispersed system.
At present, preparing conductive plastics is generally directly by graphitized carbon black or metal-powder etc. and plastic blend.For example, CN 101565542A discloses a kind of conductive MC nylon material and production method thereof, relates to the high pressure wire-crossing wheel in electric power facility, or the technical field such as Radio frequency interference.Comprise the following steps: first nylon monomer is put into to the crucible hot melt, then vacuum hydro-extraction, then add successively catalyzer, electrically conductive graphite, then carry out adding promotor after vacuum hydro-extraction, casting in mould, thermal treatment, carry out precision work again, forms finished product.The shortcoming of these class methods is: carbon black and metal-powder are difficult for adding; Disperse uneven; To the matrix physical and mechanical properties, destroy larger; Production environment is polluted large.
In addition, CN 101870812A provide a kind of conductive nylon 66 material and preparation method thereof, and the weight percent of its each component is: nylon 6680%-95%; Carbon nanotube 1%-10%; Nano imvite 1%-15%; Compatible toughening agents 1%-10.5%; Oxidation inhibitor 0.3%-1%; Nucleator 0.3%-1%; Lubricant 0.3%-1%.Its preparation method is: first by carbon nanotube, nano imvite and account for the compatible toughening agents of gross weight 0.5%-3.75%, the nylon 66 material of 5%-20% mixes, prepare master batch with Banbury mixer or twin screw extruder, then by master batch and remaining nylon 66 and compatible toughening agents and oxidation inhibitor, nucleator and mix lubricant, through twin screw extruder, extrude.But there is certain problem in this material at aspects such as elasticity, fatigue resistances.
Nylon (Nylon), the Chinese name polymeric amide, English name Polyamide (be called for short PA), be on molecular backbone chain, contain recurring amide radical group-[NHCO]-the thermoplastic resin general name.Its name by synthon concrete carbonatoms determine, as: nylon-6,66,1010,610 etc.Wherein, nylon 6 has superior over-all properties, comprises physical strength, rigidity, toughness, mechanical shock absorption and wear resistance.The research and development of electroconductive nylon 6 are also one of focuses of research and development at present.For example: CN 102108126A relates to a kind of preparation method of nylon-6 conductive microsphere, at first vinylbenzene carries out radical polymerization in the hexanolactam fused solution, then graphite oxide colloid suspension liquid joins in above-mentioned hexanolactam mixed solution, hexanolactam original position anionic ring-opening polymerization is prepared into nylon monomer-cast nylon 6/ polystyrene/graphite oxide trielement composite material, above-mentioned matrix material is pulverized, remove the continuous phase of polystyrene by dissolution with solvents, obtain nylon-6 conductive microsphere.The electroconductive nylon 6 material conductivities that the method makes are better, but physical and mechanical properties is poor, therefore have certain application limitation.
Therefore, existing conductive plastics has the wire performance or/and mechanical property is not ideal enough, has the problems such as environmental pollution.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of conductive nylon plastic.Described conductive nylon plastic comprises by mass percentage:
Polymer support 65～90%
Graphitized carbon black 5～30%
Properties-correcting agent 0.05～3%.
Preferably, described conductive nylon plastic comprises by mass percentage:
Further preferably, described conductive nylon plastic comprises by mass percentage:
Particularly preferably, described conductive nylon plastic comprises by mass percentage:
Described polymer support can also comprise the polymkeric substance that other are suitable, and such as polystyrene etc., the those skilled in the art can be selected according to the expertise of its grasp.
Preferably, described nylon 6 is the extrusion grade polymeric amide, for example the B40L of German BASF or/and with the nylon 6 of the B40L ad eundem of German BASF.
Preferably, in the mixture of described polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene: the mass ratio of Research of Grafting Malaic Anhydride Onto Polyethylene is 3: 1～1: 3, more preferably 2: 1～1: 2, is particularly preferably 1: 1.
Preferably, described polyethylene is linear polyethylene, is particularly preferably LLDPE, for example China Petrochemical Industry 7042 or/and with the LLDPE of 7042 ad eundems.
Research of Grafting Malaic Anhydride Onto Polyethylene is the known material in affiliated field, can obtain or be obtained according to prior art/new technology is synthetic by one of ordinary skill in the art by commercially available.
Preferably, described graphitized carbon black is that oil-absorption(number) (DBP) is the above graphitized carbon black of 150ml/100g, and further preferably oil-absorption(number) (DBP) is more than 180ml/100g, and particularly preferably oil-absorption(number) (DBP) is more than 200ml/100g.
Preferably, described properties-correcting agent is coupling agent, is particularly preferably titanate coupling agent.
Preferably, described processing aid comprises a kind or the combination of at least 2 kinds in polyethylene wax, Zinic stearas, dispersion agent; The example of described dispersion agent has: water glass, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99 and trisodium phosphate, triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum, fatty acid polyglycol ester etc.; Described combination typical case but the example of non-limit have: the combination of polyethylene wax, Zinic stearas, sodium lauryl sulphate, the combination of polyethylene wax, polyacrylamide, the combination of polyethylene wax, Zinic stearas, trisodium phosphate, methyl amyl alcohol, the combination of Zinic stearas, Sodium hexametaphosphate 99, guar gum etc.
Conductive nylon plastic of the present invention can also comprise other components, such as antioxidant, surface treatment agent, nucleator, compatible toughening agents, lubricant etc., and one of ordinary skill in the art can select according to grasped expertise.
One of purpose of the present invention also is to provide a kind of preparation method of described conductive nylon plastic, and described method comprises: get the raw materials ready according to formula, then adopt Banbury mixer banburying moulding, then make conductive nylon plastic with the twin screw extruder granulation.
The required condition of described banburying and granulation is affiliated field known technology, and one of ordinary skill in the art should determine according to prior art.
The conductive nylon plastic carbon black dispersion that adopts the method for the invention to prepare is even, and less due to the matrix physical and mechanical properties is destroyed, and therefore has good mechanical-physical mechanical property.
Compared with prior art, the present invention has following characteristics:
(1) can directly use, can no longer add any processing aid, production link and production unit in the middle of can reducing;
(2) processing fluidity is good, produces steadily;
(3) excellent electric conductivity, but production resistivity is 10
5Ω cm and following conductive nylon plastic;
(4) mechanical-physical mechanical property excellence;
(5) adopt Banbury mixer and twin screw extruder manufacture, pollution-free to production environment and surrounding environment.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
According to following formula, prepare burden: nylon 6 (B40L of German BASF) 55g, polyethylene (China Petrochemical Industry 7042) 2.5g, Research of Grafting Malaic Anhydride Onto Polyethylene (Nanjing friendly auxiliary agent chemical industry limited liability company) 7.5g, the graphitized carbon black that oil-absorption(number) (DBP) is 150ml/100g (hundred million rich auspicious (Tianjin) chemical industry company limiteds) 30g, titanate coupling agent (TM-12 of chemical industry company limited is raised in the sky, Yizheng) 3g, polyethylene wax (Chengdu is contained and risen development in science and technology company limited) 1g, Zinic stearas (the prosperous chemical industry of Gaomi City's friendship company limited) 0.5g, Sodium hexametaphosphate 99 0.5g, adopt Banbury mixer banburying moulding, make conductive nylon plastic 1 with the twin screw extruder granulation again.
Embodiment 2
According to following formula, prepare burden: nylon 6 (B40L of German BASF) 80g, polyethylene (China Petrochemical Industry 7042) 7.5g, Research of Grafting Malaic Anhydride Onto Polyethylene (Nanjing friendly auxiliary agent chemical industry limited liability company) 2.5g, the graphitized carbon black that oil-absorption(number) (DBP) is 200ml/100g (hundred million rich auspicious (Tianjin) chemical industry company limiteds) 5g, titanate coupling agent (TM-12 of chemical industry company limited is raised in the sky, Yizheng) 0.05g, polyethylene wax (Chengdu is contained and risen development in science and technology company limited) 3g, sodium lauryl sulphate 1g, oxidation inhibitor N, N '-bis--(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (Milan, Nanjing chemical industry company limited) 0.95g, adopt Banbury mixer banburying moulding, make conductive nylon plastic 2 with the twin screw extruder granulation again.
Embodiment 3
According to following formula, prepare burden: nylon 6 (B40L of German BASF) 60g, polyethylene (China Petrochemical Industry 7042) 7g, Research of Grafting Malaic Anhydride Onto Polyethylene (Nanjing friendly auxiliary agent chemical industry limited liability company) 13g, the graphitized carbon black that oil-absorption(number) (DBP) is 200ml/100g (hundred million rich auspicious (Tianjin) chemical industry company limiteds) 15g, titanate coupling agent (TM-12 of chemical industry company limited is raised in the sky, Yizheng) 1g, polyethylene wax (Chengdu is contained and risen development in science and technology company limited) 3g, Zinic stearas (the prosperous chemical industry of Gaomi City's friendship company limited) 1g, adopt Banbury mixer banburying moulding, make conductive nylon plastic 3 with the twin screw extruder granulation again.
Embodiment 4
According to following formula, prepare burden: nylon 6 (B40L of German BASF) 67g, polyethylene (China Petrochemical Industry 7042) 2g, Research of Grafting Malaic Anhydride Onto Polyethylene (Nanjing friendly auxiliary agent chemical industry limited liability company) 1g, the graphitized carbon black that oil-absorption(number) (DBP) is 180ml/100g (hundred million rich auspicious (Tianjin) chemical industry company limiteds) 20g, titanate coupling agent (TM-12 of chemical industry company limited is raised in the sky, Yizheng) 2g, polyethylene wax (Chengdu is contained and risen development in science and technology company limited) 4g, Zinic stearas (the prosperous chemical industry of Gaomi City's friendship company limited) 1g, tripoly phosphate sodium STPP 3g, adopt Banbury mixer banburying moulding, make conductive nylon plastic 4 with the twin screw extruder granulation again.
Embodiment 5
According to following formula, prepare burden: nylon 6 (B40L of German BASF) 80g, polyethylene (China Petrochemical Industry 7042) 2g, Research of Grafting Malaic Anhydride Onto Polyethylene (Nanjing friendly auxiliary agent chemical industry limited liability company) 3g, the graphitized carbon black that oil-absorption(number) (DBP) is 210ml/100g (hundred million rich auspicious (Tianjin) chemical industry company limiteds) 10g, titanate coupling agent (TM-12 of chemical industry company limited is raised in the sky, Yizheng) 2g, Zinic stearas (the prosperous chemical industry of Gaomi City's friendship company limited) 3g, adopt Banbury mixer banburying moulding, then make conductive nylon plastic 5 with the twin screw extruder granulation.
The prepared conductive nylon plastic of embodiment 1-5 is tested, and result is as follows:
| Parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength (MPa) | ?40 | ?60 | ?45 | ?50 | ?61 |
| Flexural strength (MPa) | ?62 | ?80 | ?60 | ?55 | ?85 |
| Modulus in flexure (MPa) | ?2450 | ?3500 | ?2780 | ?2800 | ?3600 |
| Notched Izod impact strength (kJ/m 2) | ?15 | ?5 | ?10 | ?8 | ?5 |
| Specific conductivity (Ω cm) | ?10 3 | ?10 9 | ?10 5 | ?10 4 | ?10 6 |
From above experimental data, conductive nylon material of the present invention has excellent physical and mechanical properties, simultaneously excellent electric conductivity.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (16)
1. a conductive nylon plastic comprises by mass percentage:
Wherein, described polyethylene is linear low density polyethylene.
2. conductive nylon plastic as claimed in claim 1, is characterized in that, described conductive nylon plastic comprises by mass percentage:
3. conductive nylon plastic as claimed in claim 1, is characterized in that, described conductive nylon plastic comprises by mass percentage:
4. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, described nylon 6 is the extrusion grade polymeric amide.
5. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, the B40L that described nylon 6 is German BASF or/and with the nylon 6 of the B40L ad eundem of German BASF.
6. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, in the mixture of described polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene: the mass ratio of Research of Grafting Malaic Anhydride Onto Polyethylene is 3:1～1:3.
7. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, in the mixture of described polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene: the mass ratio of Research of Grafting Malaic Anhydride Onto Polyethylene is 2:1～1:2.
8. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, in the mixture of described polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene, polyethylene: the mass ratio of Research of Grafting Malaic Anhydride Onto Polyethylene is 1:1.
9. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, described polyethylene is that China Petrochemical Industry 7042 is or/and the LLDPE of ad eundem.
10. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, described graphitized carbon black is that oil-absorption(number) is the above graphitized carbon black of 150ml/100g.
11. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, the oil-absorption(number) of described graphitized carbon black is more than 180ml/100g.
12. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, the oil-absorption(number) of described graphitized carbon black is more than 200ml/100g.
13. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, described properties-correcting agent is coupling agent.
14. as the described conductive nylon plastic of claim 1-3 any one, it is characterized in that, described properties-correcting agent is titanate coupling agent.
15. conductive nylon plastic, is characterized in that as claimed in claim 2 or claim 3, described processing aid comprises a kind or the combination of at least 2 kinds in polyethylene wax, Zinic stearas, dispersion agent.
16. the preparation method as the described conductive nylon plastic of claim 1-15 any one, is characterized in that, described method comprises: get the raw materials ready according to formula, then adopt Banbury mixer banburying moulding, then make conductive nylon plastic with the twin screw extruder granulation.
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| CN201210002707.7A CN102532882B (en) | 2012-01-05 | 2012-01-05 | Conductive nylon plastic and preparation method thereof |
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| CN201210002707.7A CN102532882B (en) | 2012-01-05 | 2012-01-05 | Conductive nylon plastic and preparation method thereof |
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| CN105694412A (en) * | 2012-08-20 | 2016-06-22 | 冯林 | Conducting engineering plastic |
| CN107674364A (en) * | 2017-08-24 | 2018-02-09 | 厦门建霖健康家居股份有限公司 | A kind of plastic material, plastic material preparation method and semidry method electroplating technology |
| CN107904740A (en) * | 2017-12-19 | 2018-04-13 | 江阴市强力化纤有限公司 | A kind of dipped type cord fabric destatics braid over braid and its production method |
| CN108193304A (en) * | 2017-12-19 | 2018-06-22 | 江阴市强力化纤有限公司 | A kind of 6 silk thread of static conductive nylon and its production method |
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| DE19854819A1 (en) * | 1998-11-27 | 2000-05-31 | Degussa | Hollow article with antistatic properties |
| FR2892173B1 (en) * | 2005-10-18 | 2007-12-14 | Arkema Sa | ANTISTATIC MULTILAYER TUBE BASED ON POLYAMIDE FOR THE TRANSFER OF FLUIDS |
| CN101230163A (en) * | 2008-02-19 | 2008-07-30 | 陆校会 | Absorbent masterbatch and production method thereof |
| CN101407632B (en) * | 2008-11-14 | 2011-01-12 | 佛山市顺德区高怡新塑料有限公司 | Conductive and antistatic nylon |
| CN102260406B (en) * | 2011-07-05 | 2013-01-30 | 南京理工大学 | MC nylon nano conductive composite material and preparation method thereof |
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