CN103265698B - Method for preparing intercalation nanocomposite material of polyaniline or polyaniline derivative, and inorganic clay by mechanochemical polymerization method - Google Patents
Method for preparing intercalation nanocomposite material of polyaniline or polyaniline derivative, and inorganic clay by mechanochemical polymerization method Download PDFInfo
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- CN103265698B CN103265698B CN201310160258.3A CN201310160258A CN103265698B CN 103265698 B CN103265698 B CN 103265698B CN 201310160258 A CN201310160258 A CN 201310160258A CN 103265698 B CN103265698 B CN 103265698B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 45
- 239000004927 clay Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 18
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 16
- 238000009830 intercalation Methods 0.000 title claims abstract description 13
- 230000002687 intercalation Effects 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 9
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052621 halloysite Inorganic materials 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052622 kaolinite Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 230000000873 masking effect Effects 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- NAZDVUBIEPVUKE-UHFFFAOYSA-N 2,5-dimethoxyaniline Chemical compound COC1=CC=C(OC)C(N)=C1 NAZDVUBIEPVUKE-UHFFFAOYSA-N 0.000 claims description 5
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 3
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 claims description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 3
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 150000001448 anilines Chemical class 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 2
- 239000001230 potassium iodate Substances 0.000 description 2
- 229940093930 potassium iodate Drugs 0.000 description 2
- 235000006666 potassium iodate Nutrition 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses an intercalation nanocomposite material of a polyaniline or a polyaniline derivative, and inorganic clay by mechanochemical polymerization method. The method comprises the following steps of: (1) placing inorganic clay into a round-bottom flask with a branch port, vacuum-pumping, fully filling with argon, adding aniline or an aniline derivative, wrapping a tin foil out of the round-bottom flask after magnetically stirring, and stewing out of light under normal temperature, to obtain a blending fluid suspension; (2) grinding the blending fluid suspension, adding an oxidizing agent, covering a mortar with a tunnel in a grinding process, introducing argon into one end of the tunnel, continuously grinding, until to become atropurpureus completely; and (3) washing after reaction, filtrating, and vacuum-drying until constant weight, to obtain the intercalation nanocomposite material of inorganic clay. The prepared nanocomposite not only makes polyaniline or the polyaniline derivative have good dispersibility and high mechanical strength, but also raises water solubility and processing temperature of polyaniline or the polyaniline derivative. The method has advantages of simple preparation method and high polymer intercalation rate, and has a practical application meaning.
Description
Technical field
The present invention relates to a kind of method that mechanochemistry polymerization prepares the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay.
Background technology
Polyaniline is a kind of common conducting high polymers thing, not only has the electroconductibility of metal and the workability of plastics, also possesses chemistry and chemical property that metal and plastics are short of, and its abundant raw material source, be cheaply easy to get, synthesis is convenient.Have a wide range of applications in marine anticorrosion and anti-fouling material, electromagnetic shielding and absorbing material etc., therefore polyaniline becomes one of conductive polymers of most commercial viability.
But due to the rigidity of polyaniline, make its solvability and melt and dissolved performance all very poor, be dissolved in any solvent hardly, so just limit its application.The method that bibliographical information adopts aniline ortho position or position to modify, adopts the doping of function protonic acid, adopts graft copolymerization, and the method such as in-situ polymerization in inorganic clay, carries out modification to aniline.But there is complicated process of preparation, and be difficult to obtain the compound of inorganic-organic thing on nano-scale.
Intercalation polymeric can realize organism matrix and the compound of inorganics disperse phase on nanoscale, the toughness of the rigidity of inorganics, dimensional stability and thermostability and polymkeric substance, workability and dielectricity can ideally combine by the polymer/laminated inorganic clay compound material of gained, are different from common polymer/inorganic filler compound system.
Compared to conventional electrochemistry and chemical polymerization, mechanochemistry polymerization has that preparation time is short, preparation process environmental protection, prepare the advantages such as simple.Be a kind of gentleness, easily operate and realize the polymerization process of suitability for industrialized production.
Summary of the invention
A kind of mechanochemistry polymerization is the object of the present invention is to provide to prepare the method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay.
The step preparing the method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay by mechanochemistry polymerization is as follows:
1) inorganic clay is put into the round-bottomed flask of a band mouth, vacuumize applying argon gas 2 ~ 3 times, 0.05 ~ 4.5 times of monomer being equivalent to inorganic clay weight is added with syringe, monomer is aniline or anils, after magnetic agitation, round-bottomed flask outer cladding masking foil, normal temperature lucifuge is placed 24 ~ 48 hours, obtains blended suspension;
2) by blended suspension mortar grinder 5 ~ 10 minutes, add oxygenant, the mol ratio of oxygenant and monomer is 1:10 ~ 3:2, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, continues grinding 0.5 ~ 1.2 hour, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains the intercalated nano-composite of inorganic clay.
Described inorganic clay is polynite, kaolinite clay or halloysite, and particle size is nanometer or micron order.Described anils is 2,5-dimethoxyaniline, 2-aminotoluene, 3-monomethylaniline, 2-anisidine, 2-fluoroaniline, 2-benzaminic acid or 2-aniline sulfonic acid.Described oxygenant is one or more in persulphate, dichromate or iodate.Described polyaniline or the polyaniline derivative intercalation rate in inorganic clay is 85 ~ 99%.
The present invention proposes a kind of prepare modified polyaniline material brand-new scheme, the method namely utilizing inorganic clay and aniline or anils to be polymerized by mechanochemistry carries out modification.Conventional electrochemistry and chemical polymerization are compared in mechanochemistry polymerization, have that preparation time is short, preparation process environmental protection, prepare simple, technical process simple, polyaniline or polyaniline derivative intercalation rate advantages of higher in inorganic clay.The polyaniline or the polyaniline derivative that are not easy insertion inorganic clay interlayer under machinery polymerization makes other reaction environment by additional mechanical force can insert its interlayer effectively.The interlamellar spacing that inorganic clay is less in addition makes to insert aniline therebetween or anils can only be strand polymerization, can change polyaniline and the original physico-chemical property of polyaniline derivative thereof to a great extent by this guidance quality synthesis.Compare other existing preparation method, preparation method of the present invention has the meaning of practical application more.
Embodiment
In the present invention, inorganic clay is polynite, kaolinite clay or halloysite, and particle size is nanometer or micron order.Anils is 2,5-dimethoxyaniline, 2-aminotoluene, 3-monomethylaniline, 2-anisidine, 2-fluoroaniline, 2-benzaminic acid or 2-aniline sulfonic acid.Oxygenant is one or more in persulphate, dichromate or iodate.Just become polyaniline and polyaniline derivative after aniline or anils insert clay, polyaniline or the polyaniline derivative intercalation rate in inorganic clay is 85 ~ 99%.
Embodiment 1
1) polynite is put into the round-bottomed flask of a band mouth, vacuumize applying argon gas 2 times, add the 0.05 times of aniline being equivalent to polynite weight with syringe, after magnetic agitation, round-bottomed flask outer cladding masking foil, normal temperature lucifuge places 24 hours, obtains blended suspension;
2) by blended suspension mortar grinder 5 minutes, add ammonium persulphate, the mol ratio of ammonium persulphate and aniline is 1:10, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, continues grinding 0.5 hour, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains Preparation of Polymer/Montmorillonite Nano.The intercalation rate of described polyaniline in polynite is 99%.
Embodiment 2
1) kaolinite clay is put into the round-bottomed flask of a band mouth, vacuumize applying argon gas 3 times, add 4.5 times 2 that is equivalent to kaolinite clay weight, 5-dimethoxyaniline, after magnetic agitation, round-bottomed flask outer cladding masking foil, normal temperature lucifuge places 48 hours, obtains blended suspension;
2) by blended suspension mortar grinder 10 minutes, add potassium bichromate, the mol ratio of potassium bichromate and 2,5-dimethoxyaniline is 3:2, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, continues grinding 1.2 hours, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains kaolinite clay intercalated nano-composite.The described poly-intercalation rate of 2,5-dimethoxyaniline in kaolinite is 85%.
Embodiment 3
1) halloysite is put into the round-bottomed flask of a band mouth, vacuumize applying argon gas 3 times, add the 0.5 times of aniline being equivalent to halloysite weight with syringe, magnetic agitation, makes it blended, round-bottomed flask outer cladding masking foil, and normal temperature lucifuge places 24 hours;
2) by blended suspension mortar grinder 5 minutes, add Potassium Persulphate, the mol ratio of Potassium Persulphate and aniline is 1:1, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, and continue grinding, milling time is 0.5 hour, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains halloysite clay intercalated nano-composite.The intercalation rate of described polyaniline in halloysite is 90%.
Embodiment 4
1) polynite is put into the round-bottomed flask of a band mouth, vacuumize applying argon gas 3 times, add the 3-monomethylaniline of 1.5 times that are equivalent to polynite weight with syringe, magnetic agitation, makes it blended, round-bottomed flask outer cladding masking foil, and normal temperature lucifuge places 24 hours;
2) by blended suspension mortar grinder 5 minutes, add Potassium Iodate, the mol ratio of Potassium Iodate and 3-monomethylaniline is 1:3, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, and continue grinding, milling time is 0.7 hour, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains Preparation of Polymer/Montmorillonite Nano.The intercalation rate of described polyaniline in polynite is 92%.
Claims (2)
1. prepare a method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay by mechanochemistry polymerization, it is characterized in that its step is as follows:
1) inorganic clay is put into the round-bottomed flask of a band mouth, vacuumize and applying argon gas 2 ~ 3 times, 0.05 ~ 4.5 times of monomer being equivalent to inorganic clay weight is added with syringe, monomer is aniline or anils, after magnetic agitation, round-bottomed flask outer cladding masking foil, normal temperature lucifuge is placed 24 ~ 48 hours, obtains blended suspension;
2) by blended suspension mortar grinder 5 ~ 10 minutes, add oxygenant, the mol ratio of oxygenant and monomer is 1:10 ~ 3:2, in process of lapping, covers mortar with funnel, and funnel one end leads to argon gas, continues grinding 0.5 ~ 1.2 hour, to becoming atropurpureus completely;
3) after reaction terminates, use water and absolute ethanol washing respectively, filter, vacuum-drying, to constant weight, obtains the intercalated nano-composite of inorganic clay;
Described anils is 2,5-dimethoxyaniline, 2-aminotoluene, 3-monomethylaniline, 2-anisidine, 2-fluoroaniline, 2-benzaminic acid or 2-aniline sulfonic acid.
2. a kind of mechanochemistry polymerization according to claim 1 prepares the method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay, it is characterized in that described inorganic clay is polynite, kaolinite clay or halloysite, particle size is nanometer or micron order.
3.a kind of mechanochemistry polymerization according to claim 1 prepares the method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay, it is characterized in that described oxygenant is one or more in persulphate, dichromate or iodate.
4.a kind of mechanochemistry polymerization according to claim 1 prepares the method for the intercalated nano-composite of polyaniline or polyaniline derivative and inorganic clay, it is characterized in that described polyaniline or the polyaniline derivative intercalation rate in inorganic clay is 85 ~ 99%.
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