CN106750287A - A kind of preparation method of polypyrrole/stalk conducing composite material - Google Patents

A kind of preparation method of polypyrrole/stalk conducing composite material Download PDF

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Publication number
CN106750287A
CN106750287A CN201611085046.3A CN201611085046A CN106750287A CN 106750287 A CN106750287 A CN 106750287A CN 201611085046 A CN201611085046 A CN 201611085046A CN 106750287 A CN106750287 A CN 106750287A
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stalk
polypyrrole
composite material
dry
conducing composite
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CN106750287B (en
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臧利敏
杨超
周焕福
徐旭
范辂
胡晓明
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Guilin University of Technology
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a kind of preparation method of polypyrrole/stalk conducing composite material.The stalk after crushing is washed first, dry, it is subsequently adding deionized water and pyrrole monomer, it is sufficiently stirred for dispersion, ammonium persulfate solution is added, by oxidation polymerization so that polypyrrole is coated on stalk particle surface, suction filtration is simultaneously washed with deionized, finally vacuum drying can obtain polypyrrole/stalk conducing composite material, and the polypyrrole/stalk conducing composite material can act as conductive filler and use.Prepared by the present invention polypyrrole is coated on powder of straw surface, and the conductive filler of preparation has conductance very high, and straw environment protection is easy to get, and cost is relatively low, is adapted to large-scale production.

Description

A kind of preparation method of polypyrrole/stalk conducing composite material
Technical field
The invention belongs to technical field of polymer composite materials, more particularly to a kind of polypyrrole/stalk conducing composite material Preparation method.
Background technology
Conducting polymer is typically insoluble insoluble, and it significantly limit the processing and extensive use of conducting polymer. Therefore, since the later stage eighties 20th century, the machinability of conducting polymer has been improved, further to realize conducting polymer material The industrial applications of material, an important research developing way as conducting polymer.Polypyrrole (PPy) is used as typical conductive Macromolecular material is always one of focus of the area research, but its major defect be indissoluble solution, infusibility melt, poor processability, Limit its extensive use.To overcome this shortcoming to improve its machining property, conducting polymer composite material is prepared, It is the important method for improving its processing characteristics at present.Many research groups are by polypyrrole and carbon black, silica, Graphene, poly- The Material claddings such as styrene, fabric etc. are powdered, film-form, threadiness, this method had both solved the processing problems of material, and The mechanical property of material is improved to a certain extent.Prepare Pt/Polypyrrole composite material mainly include cladded type, intercal type and Conductive polymer nanometer composite material of the surface with functional group, and based on cladded type, i.e., organic monomer is micro- in solid Grain surface aggregate coats one layer of conducting polymer, to reach the physical and mechanical properties and conducting polymer electric conductivity of solia particle With reference to purpose.The material of these conducting polymers cladding can be as the filler with conducting function.
People mix the metal dusts such as the good silver powder of electric conductivity, copper powder and nickel powder and are filled out as conduction in the polymer earliest Material, when making filler with macromolecule matrix blending with them, it is possible to achieve preferable mixing uniformity.But these metal dusts Conductive additive has poor dispersion in the base, is easily oxidized and the low problem of conductance, and metallic fiber can also add Enter in additive, but there is the defects such as cost price is high.
The present invention plans polypyrrole and is coated on powder of straw surface, prepares a kind of new conducing composite material, and the conduction is multiple Condensation material has conductance very high, and straw environment protection is easy to get, and cost is relatively low, is adapted to large-scale production.At present, using poly- pyrrole Cough up to be coated on powder of straw surface and prepare conducing composite material and have not been reported.
The content of the invention
The conductive filler conductance that the purpose of the present invention is directed at present on the market is not high, and property is unstable, relatively costly, close Spend the defect such as big, there is provided a kind of preparation method of polypyrrole/stalk conducing composite material.
Thinking of the present invention：The stalk after crushing is washed first, is dried, be subsequently adding deionized water and pyrrole monomer, filled Divide dispersed with stirring, add ammonium persulfate solution, by oxidation polymerization so that polypyrrole is coated on stalk particle surface, suction filtration is simultaneously It is washed with deionized, finally vacuum drying can obtain polypyrrole/stalk conducing composite material.
Concretely comprise the following steps:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) raw material is weighed according to following parts by weight, 10 ~ 100 parts of dry stalk powder obtained in step (1), pyrroles 1 ~ 50 parts, 10 ~ 500 parts of the ammonium persulfate aqueous solution of 10 wt%, 1000 ~ 5000 parts of deionized water.
(3) raw material that step (2) is weighed is followed the steps below into operation, dry stalk powder is soaked with deionized water Not yet, after being subsequently adding pyrrolo- stirring 1h, system is maintained at 25 DEG C, and 10 wt% ammonium persulfate aqueous solutions are added dropwise to thereto, protects Hold 25 DEG C and continue stirring reaction 5 hours, suction filtration, then cleaned 3 times with the ethanol water of 30 wt%, finally cleaned with distilled water Become to filtrate and clarify, gained solid product dries 24h in 55 DEG C of electric drying oven with forced convection, cool down, that is, polypyrrole/straw are obtained Stalk conducing composite material.
Obtained polypyrrole/stalk conducing composite material of the invention is used as conductive filler.
Compared with prior art, advantage of the invention is that:
1st, raw material stalk is agricultural wastes, cheap and easy to get, and wide material sources are prepared into conducing composite material, meet environment Close friend, utilization of resources theory.
2nd, preparation technology used is easy to operate, simple and easy to apply.
3rd, proposition polypyrrole cladding stalk is used to prepare conductive material first, prepares a kind of good new of conductive effect Type conductive material, has practical significance to development conductive material new technology.
4th, the obtained conducing composite material of the present invention belongs to environmentally friendly material, and non-secondary pollution is produced.
Specific embodiment mode
The present invention is further elaborated below by specific embodiment, in order to skilled artisan understands that originally Invention.
Embodiment 1:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) dry stalk powder obtained in 10 mass parts steps (1) is submerged with 5000 mass parts deionized waters, plus After entering the pyrrolo- stirring 1h of 50 mass parts, system is maintained at 25 DEG C, and the persulfuric acid of the wt% of 500 mass parts 10 is added dropwise to thereto Aqueous ammonium, is kept for 25 DEG C simultaneously continue stirring reaction 5 hours, suction filtration, then cleans 3 times with the ethanol water of 30 wt%, finally Cleaned to filtrate to become with distilled water and clarified, gained solid product dries 24h in 55 DEG C of electric drying oven with forced convections, cooled down, that is, made Obtain polypyrrole/stalk conducing composite material.
Polypyrrole obtained in the present embodiment/stalk conducing composite material is tested with four probe pressed disc methods, its electrical conductivity is 1.1 S/cm.By the conducing composite material with it is polypropene blended, by polypyrrole/stalk conducing composite material:Polypropylene (weight ratio)=3: 7, print is compressed into tablet form, test volume resistivity is 7.2 × 104 Ω·m。
Embodiment 2:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) dry stalk powder is submerged with 1000 mass parts deionized waters obtained in by 10 mass parts the step of (1), plus After entering the pyrrolo- stirring 1h of 1 mass parts, system is maintained at 25 DEG C, and the ammonium persulfate of the wt% of 10 mass parts 10 is added dropwise to thereto The aqueous solution, is kept for 25 DEG C and continues stirring reaction 5 hours, suction filtration, then is cleaned 3 times with the ethanol water of 30 wt%, is finally used Distilled water is cleaned to filtrate to become and clarified, and gained solid product dries 24h in 55 DEG C of electric drying oven with forced convections, is cooled down, that is, be obtained Polypyrrole/stalk conducing composite material.
Four probe pressed disc methods test polypyrrole obtained in the present embodiment/stalk conducing composite material, and its electrical conductivity is 4.2 × 10-4 S/cm.By the conducing composite material with it is polypropene blended, by polypyrrole/stalk conducing composite material:Polypropylene (weight Than)=3:7, print is compressed into tablet form, test volume resistivity is 2.5 × 107 Ω·m。
Embodiment 3:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) dry stalk powder obtained in 100 mass parts steps (1) is submerged with 5000 mass parts deionized waters, plus After entering the pyrrolo- stirring 1h of 50 mass parts, system is maintained at 25 DEG C, and the persulfuric acid of the wt% of 500 mass parts 10 is added dropwise to thereto Aqueous ammonium, is kept for 25 DEG C simultaneously continue stirring reaction 5 hours, suction filtration, then cleans 3 times with the ethanol water of 30 wt%, finally Cleaned to filtrate to become with distilled water and clarified, gained solid product dries 24h in 55 DEG C of electric drying oven with forced convections, cooled down, that is, made Obtain polypyrrole/stalk conducing composite material.
Four probe pressed disc methods test polypyrrole obtained in the present embodiment/stalk conducing composite material, and its electrical conductivity is 3.7 × 10-2cm/S.By the polypyrrole/stalk conducing composite material with it is polypropene blended, by polypyrrole/stalk conducing composite material:It is poly- Propylene (weight ratio)=3:7, print is compressed into tablet form, test volume resistivity is 5.3 × 106 Ω·m。
Embodiment 4:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) dry stalk powder obtained in 100 mass parts steps (1) is submerged with 5000 mass parts deionized waters, plus After entering the pyrrolo- stirring 1h of 50 mass parts, system is maintained at 25 DEG C, and the persulfuric acid of the wt% of 10 mass parts 10 is added dropwise to thereto Aqueous ammonium, is kept for 25 DEG C simultaneously continue stirring reaction 5 hours, suction filtration, then cleans 3 times with the ethanol water of 30 wt%, finally Cleaned to filtrate to become with distilled water and clarified, gained solid product dries 24h in 55 DEG C of electric drying oven with forced convections, cooled down, that is, made Obtain polypyrrole/stalk conducing composite material.
Four probe pressed disc methods test polypyrrole obtained in the present embodiment/stalk conducing composite material, and its electrical conductivity is 5.1 × 10-5cm/S.By the polypyrrole/stalk conducing composite material with it is polypropene blended, by polypyrrole/stalk conducing composite material:It is poly- Propylene (weight ratio)=3:7, print is compressed into tablet form, test volume resistivity is 9.6 × 108 Ω·m。
Embodiment 5:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained.
(2) dry stalk powder obtained in 100 mass parts steps (1) is submerged with 5000 mass parts deionized waters, plus After entering the pyrrolo- stirring 1h of 30 mass parts, system is maintained at 25 DEG C, and the persulfuric acid of the wt% of 500 mass parts 10 is added dropwise to thereto Aqueous ammonium, is kept for 25 DEG C and continues stirring reaction 5 hours, suction filtration, then is cleaned 3 times with the ethanol solution of 30 wt%, is finally used Distilled water is cleaned to filtrate to become and clarified, and gained solid product dries 24h in 55 DEG C of electric drying oven with forced convections, is cooled down, that is, be obtained Polypyrrole/stalk conducing composite material.
Four probe pressed disc methods test polypyrrole obtained in the present embodiment/stalk conducing composite material, and its electrical conductivity is 7.4 × 10-3cm/S.By the polypyrrole/stalk conducing composite material with it is polypropene blended, by polypyrrole/stalk conducing composite material:It is poly- Propylene (weight ratio)=3:7, print is compressed into tablet form, test volume resistivity is 2.8 × 107Ω·m。

Claims (1)

1. the preparation method of a kind of polypyrrole/stalk conducing composite material, it is characterised in that concretely comprise the following steps:
(1) crushed with pulverizer after dry stalk being cut into segment, then cross the sub-sieve of 100 mesh, take sub-sieve lower part of screen Divide and dry 24h in 50 DEG C of electric drying oven with forced convections, dry stalk powder is obtained；
(2) raw material is weighed according to following parts by weight, 10 ~ 100 parts of dry stalk powder obtained in step (1), pyrroles 1 ~ 50 Part, 10 ~ 500 parts of the ammonium persulfate aqueous solution of 10 wt%, 1000 ~ 5000 parts of deionized water；
(3) raw material that step (2) is weighed is followed the steps below into operation, dry stalk powder is submerged with deionized water, After being subsequently adding pyrrolo- stirring 1h, system is maintained at 25 DEG C, and 10 wt% ammonium persulfate aqueous solutions are added dropwise to thereto, keeps 25 DEG C and continue stirring reaction 5 hours, suction filtration, then cleaned 3 times with the ethanol water of 30 wt% is finally cleaned to filter with distilled water Liquid becomes clarification, and gained solid product dries 24h in 55 DEG C of electric drying oven with forced convection, cools down, that is, polypyrrole/stalk is obtained and leads Composite.
CN201611085046.3A 2016-12-01 2016-12-01 A kind of preparation method of polypyrrole/stalk conducing composite material Active CN106750287B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250559A (en) * 2018-03-05 2018-07-06 象山杰尔德智能科技有限公司 A kind of high-performance rotational moulding type urea box and preparation method thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101251506A (en) * 2008-03-15 2008-08-27 西北师范大学 Method for manufacturing conductive polyaniline/cellulose composite biosensor
CN105348526A (en) * 2015-11-20 2016-02-24 青岛理工大学 Polypyrrole @ graphene conductive pressure-sensitive composite material and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101251506A (en) * 2008-03-15 2008-08-27 西北师范大学 Method for manufacturing conductive polyaniline/cellulose composite biosensor
CN105348526A (en) * 2015-11-20 2016-02-24 青岛理工大学 Polypyrrole @ graphene conductive pressure-sensitive composite material and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吴谦: ""导电聚合物/纤维素纳米晶复合材料的制备与性能"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250559A (en) * 2018-03-05 2018-07-06 象山杰尔德智能科技有限公司 A kind of high-performance rotational moulding type urea box and preparation method thereof

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