CN113754885B - Preparation method and application of low-cost high-purity polymelamine - Google Patents
Preparation method and application of low-cost high-purity polymelamine Download PDFInfo
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- 229920000580 poly(melamine) Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 10
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229940068041 phytic acid Drugs 0.000 claims description 10
- 235000002949 phytic acid Nutrition 0.000 claims description 10
- 239000000467 phytic acid Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 40
- 238000006116 polymerization reaction Methods 0.000 abstract description 34
- 230000001590 oxidative effect Effects 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- 238000001757 thermogravimetry curve Methods 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000006184 cosolvent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004573 interface analysis Methods 0.000 description 1
- ZEKZLJVOYLTDKK-UHFFFAOYSA-N lomefloxacin Chemical compound FC1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNC(C)C1 ZEKZLJVOYLTDKK-UHFFFAOYSA-N 0.000 description 1
- 229960002422 lomefloxacin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- -1 melamine amine Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 238000000782 polymeric membrane extraction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a preparation method and application of low-cost and high-purity polymelamine. The method takes melamine as a monomer and adopts an oxidative polymerization method to prepare the poly-melamine. The invention not only greatly improves the production efficiency of the poly-melamine, meets the requirement of industrial production, but also does not need to consume a large amount of electric energy, does not need to use equipment such as an electrochemical workstation and the like, does not need to use expensive consumables such as electrodes and the like, has simple and convenient preparation process and low production cost. The obtained poly-melamine has high purity, the crystal size can reach 3-10 mu m, the density and mechanical property of the poly-melamine can be improved, the practical application range of the poly-melamine on composite electrode materials, electronic devices and sensors is expanded, and the poly-melamine has great potential and good market prospect for realizing industrial production.
Description
Technical Field
The invention belongs to the technical field of polymer development, and particularly relates to a preparation method and application of low-cost high-purity polymelamine.
Background
The poly (melamine) (PME) is a novel conductive polymer and has the advantages of good stability, high nitrogen content, rich amino groups and the like. The PME has good stability, has stronger adhesive force with the surface of the electrode, contains abundant nitrogen atoms, amino groups and other advantages, so that the PME is widely applied to electrode modification; the electrode modified by the PME can be applied to an electrochemical sensor for detecting DNA, bisphenol A, drug molecules, gallic acid, hydroquinone multiple isomers, neurotransmitters and the like, so the PME has wide application prospects in the aspects of sensors, photoelectrocatalysis, color-changing devices, battery materials and the like.
At present, the electrochemical polymerization method of monomer MA is adopted in all reports of polymelamine. According to the invention, patent CN109358102A discloses a method for rapidly preparing a conductive polymer electrode of poly (melamine) and application thereof, wherein melamine is taken as a monomer, water is taken as a solvent, glassy carbon is taken as a working electrode, the conductive polymer electrode of poly (melamine) can be rapidly prepared under the condition of solid-state electrochemical polymerization, and a conductive polymer film of poly (melamine) with redox activity is obtained on the surface of the electrode. Tsai et al reported anodic pre-oxidation of carbon electrodes in 0.1M phosphate buffer solution using a voltage of 2.0V for 300s. Subsequently, the carbon electrode was immersed in a 0.1M HCl solution containing 1.0mM melamine, and the surface of the carbon electrode was subjected to scanning at a rate of 0.1V/s in the range of 0.2V to 1.5V by cyclic voltammetry to deposit the polymelamine on the surface of the carbon electrode (Tsai H, chang C, wu L, et al, feasibility Study of Biosensors Based on Polymelamine-modified Screen-printed carbonn. electrolytes.electroanalysis.2017, 29 (9): 2053-2061.). Harsini et al reported that the carbon electrode was immersed in a 0.1M NaOH solution containing 1mM melamine, and the melamine was deposited on the surface of the carbon electrode by scanning 20 cycles at a voltage change rate of 100mV/s over a voltage range of 0 to 1.6V using cyclic voltammetry (Farida A N, fitriany E, baktir A, et al, voltammetric Study of Ascorbic Acid Using Polymelamine/Gold Nanoparticle Modified Carbon Paste electric.IOP Conference Series: earth and Environmental science.2019,217: 012004.). However, the above polymerization method has some drawbacks: first, electrochemical polymerization requires an electrochemical workstation as a polymerization device and consumes consumables such as electric energy and electrodes. Second, in electrochemical polymerization, the concentration of monomer MA is lower, resulting in lower yields of PME and higher production costs for PME. Thirdly, as the electrochemical polymerization method mainly causes monomer MA to be polymerized and deposited on the surface of the matrix electrode to form a compact polymer layer, unreacted monomer is inevitably remained in the compact polymer and is difficult to elute, so that the purity of a polymerization product is lower. Fourth, the size of the polymelamine particles prepared by electrochemical polymerization is only a few nanometers to hundreds of nanometers (Gupta P, yadav S K, goyal R N, A Sensitive Polymelamine Modified Sensor for the Determination of Lomefloxacin in Biological fluids. Journal of the Electrochemical society.2014,162 (1): H86-H92;
P,Bogdanowicz R,
melamine-modified Boron-doped Diamond towards Enhanced Detection of Adenine, related and cafeine. Electric analysis 2016,28 (1): 211-221.) whereas small-size crystalline polymelamines are inferior in density and mechanical properties, the polymelamines prepared by this method limit the practical application range thereof on composite electrode materials, electronic devices and sensors.
Oxidative polymerization refers to the polymerization under acidic conditions under the action of an oxidizing agentAnd (3) polymerizing the monomers. For example, the oxidative polymerization of aniline monomers to produce polyaniline has been reported earlier (S.N.Kumar G B, F.Gaillid, electronic and structural characterization of electrochemically synthesized conducting polyaniline from XPS publications.surface and Interface analysis.1990, 15:531.). However, the oxidative polymerization of melamine has not been reported so far, and this is mainly because: first, the disclosed aniline oxidative polymerization is almost exclusively carried out in water systems, thanks to the relatively high solubility of aniline in water, whereas the solubility of melamine in water is low, making it difficult to obtain directly in water systems a high yield of polymer like aniline. Secondly, the aniline molecule has only one amino group, the oxidation polymerization steric effect is not obvious, and the melamine molecule has three amino groups, and the steric effect is an important factor for limiting the growth of the melamine into a polymer in the oxidation polymerization process. In addition, the six-membered ring of the aniline molecule is all carbon atoms, while the six-membered ring of the melamine molecule contains three carbon atoms and three nitrogen atoms, and the nitrogen atoms with larger electronegativity have stronger electron-withdrawing effect, so that the melamine molecule is subjected to-NH 2 The reduction of melamine, leading to a decrease in the activity of oxidative polymerization of melamine, making it more difficult to obtain polymers by oxidative polymerization. Therefore, the oxidative polymerization of melamine has a great technical difficulty and is a problem to be solved at present.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method and application of low-cost and high-purity polymelamine, and solves the problems of complex process, high cost, low yield, low purity and the like existing in the existing polymelamine preparation method.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of low-cost and high-purity polymelamine, which comprises the following steps:
1) Placing melamine in a cosolvent for ultrasonic treatment until a uniform transparent solution, namely a solution A, is formed; dissolving persulfate (oxidant) in deionized water to obtain a solution B; then respectively immersing the solution A and the solution B into constant-temperature water baths with the same temperature;
2) And (3) under the condition of constant-temperature water bath, introducing inactive gas into the solution A, slowly dripping the solution B into the solution A, fully stirring the obtained mixed solution for reaction, filtering a reaction product after the reaction is finished, collecting a solid product, washing the solid product with deionized water for a plurality of times until the pH value of a washing solution is 7, and preserving the washing solution after freeze-drying to obtain the polymelamine.
Therefore, the cosolvent such as phytic acid in the invention can be well mutually dissolved with melamine on one hand, and can be well mutually dissolved with water at the same time, and the addition of the phytic acid effectively improves the solubility of the melamine in water. In another aspect, each phytic acid molecule contains 24 oxygen atoms, and each oxygen atom has two lone pairs of electrons capable of reacting with-NH on melamine molecule 2 Generating obvious coordination effect, improving the NH 2 Is a reducing and oxidative polymerization activity. Therefore, the cosolvent represented by the phytic acid provided by the invention is also an activator, and simultaneously improves the solubility of the melamine in water and the oxidative polymerization activity of the melamine, so that the melamine can be smoothly oxidized and polymerized in a water system. The sulfuric acid contains a plurality of oxygen atoms, and the activity of melamine molecules is also obviously improved. Thus, the reaction mechanism for oxidative polymerization of Melamine (MA) to obtain PME in the presence of the co-solvent phytic acid/sulfuric acid and the oxidant persulfate is as follows: as shown in FIG. 1, persulfate is hydrolyzed in the presence of water to form bisulfate and hydrogen peroxide. Hydrogen peroxide with strong oxidizing property for primary amine (-NH) on Melamine (MA) 2 ) Oxidation occurs to form a covalently linked secondary amine (-NH-), and may even further oxidize to form a tertiary amine (-n=n-), thereby effecting the linkage between the monomers and polymerizing to produce the PME.
Preferably, in step 1), the cosolvent is phytic acid or sulfuric acid; the persulfate is potassium persulfate, ammonium persulfate or sodium persulfate.
Preferably, the concentration of melamine in the solution A in the step 1) is 0.18 to 0.49mol/L; the concentration of persulfate in the solution B in the step 2) is 1.29-3.39 mol/L.
Preferably, the temperature of the constant-temperature water bath in the step 2) is 0-40 ℃, and the immersion time of the constant-temperature water bath is 20-40 min.
Preferably, the mole ratio of persulfate to melamine in the mixed solution is 3-4: 1.
preferably, the inactive gas is nitrogen, argon or helium; the inlet time of the inactive gas is 10-15 min.
Preferably, the dropping speed is 0.5 to 2 drops/sec.
Preferably, the stirring reaction time is 20 to 40 minutes.
It is a further object of the present invention to provide a polymelamine prepared by the above process.
It is a further object of the present invention to provide the use of the above-mentioned polymelamines for electrical devices or biosensing.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes melamine as a monomer for the first time, and adopts an oxidative polymerization method to prepare the poly-melamine. Wherein, the concentration of the monomer MA can reach 0.49mol/L at most, compared with the existing electrochemical polymerization method that the concentration of the monomer MA is limited (usually 1 mmol/L), the production efficiency of the poly-melamine is greatly improved, the high yield can be realized, and the method is suitable for the industrial production requirement. The oxidation polymerization method does not need to consume a large amount of electric energy, does not need to use equipment such as an electrochemical workstation and the like, does not need to use expensive consumables such as an electrode and the like, has simple and convenient preparation process, does not need to use electrolyte, is beneficial to environmental protection, has low production cost, and has great potential and good market prospect for realizing industrial production.
2. The oxidation method provided by the invention can be used for preparing the polymelamine by utilizing the solubility difference of the monomer and the polymer, and the powdery product is washed for a plurality of times, so that the residual monomer can be effectively removed, and the polymelamine with high purity can be obtained, which is difficult to realize by the traditional electrochemical polymerization method. The crystal size of the prepared poly-melamine can reach 3-10 mu m, which is far larger than the size of poly-melamine particles (about several nanometers to hundreds of nanometers) prepared by an electrochemical polymerization method, and the large-size crystal is beneficial to improving the density and mechanical properties of the poly-melamine, and expands the practical application range of the poly-melamine on composite electrode materials, electronic devices and sensors.
Drawings
FIG. 1 is a schematic representation of the mechanism of the present invention for preparing a polymelamine PME.
FIG. 2 is a polymelamine PME prepared in example 1 of the present invention 1 SEM images of (a).
FIG. 3 is a block diagram of a monomeric MA and a polymelamine PME prepared according to example 1 of the invention 1 Is a spectrum of infrared light of (a) is obtained.
FIG. 4 monomer MA and Polymelamine PME prepared according to example 1 of the present invention 1 Is a XPS full spectrum of (C).
FIG. 5 is a high resolution N1s XPS spectrum of monomer MA.
FIG. 6 is a schematic illustration of a polymelamine PME prepared according to the present invention 1 Is a high resolution N1s XPS spectrogram of (a).
FIG. 7 shows monomers MA, APS and a polymelamine PME prepared according to the invention 1 Hydrogen spectrum nuclear magnetic resonance 1 H NMR，DMSO-d 6 ) A spectrogram.
FIG. 8 is a polymelamine PME prepared in example 1 of the present invention 1 TGA profile of (c).
FIG. 9 is a polymelamine PME prepared in example 2 of the present invention 2 TGA profile of (c).
FIG. 10 is a polymelamine PME prepared in example 3 of the present invention 3 TGA profile of (c).
FIG. 11 is a polymelamine PME prepared in example 4 of the present invention 4 TGA profile of (c).
FIG. 12 is a polymelamine PME prepared in example 5 of the present invention 5 TGA profile of (c).
FIG. 13 is a polymelamine PME prepared in example 6 of the present invention 6 TGA profile of (c).
FIG. 14 is a polymelamine PME prepared in example 7 of the present invention 7 TGA profile of (c).
FIG. 15 shows the present inventionExample 8 preparation of a PolyMelamine PME 8 TGA profile of (c).
FIG. 16 is a polymelamine PME prepared in example 9 of the present invention 9 TGA profile of (c).
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the following experimental methods are not particularly described as conventional methods.
1. Method for preparing poly (melamine) PME
Example 1
1) 0.61g (4.8 mmol) of Melamine (MA) was added to 10mL of Phytic Acid (PA), and the solution was sonicated to promote the dissolution of MA in PA until a pale yellow transparent solution was formed, i.e. solution A was obtained, and then the solution A was placed in an ice-water bath for 30min.
2) 3.86g (16.9 mmol) of ammonium persulfate was dissolved in 5mL of deionized water to obtain solution B, which was then placed in an ice-water bath for 30min.
3) Under the ice water bath condition, argon is bubbled into the solution A for 10min, then the solution B is dripped into the solution A at the speed of 1 drop/second, after the solution B is completely added into the solution A, the obtained mixed solution is continuously stirred for 30min, the solid product is filtered and collected, the solid product is washed with deionized water for a plurality of times until the pH value of the washing solution is 7, and finally the product is stored after freeze-drying, and is named PME 1 。
The amounts of melamine and ammonium persulfate used in examples 2-9 were varied, the water bath conditions were specified in Table 1, and the other steps and parameters were the same as in example 1.
TABLE 1
2. Product detection
1. Using scanning electricitySub-microscope pair PME 1 The observation was carried out, and the results are shown in FIG. 2.
As can be seen, the PME 1 The cube appearance with clear edges and corners is shown, and the size of the cube is about 3-10 mu m. The size of the polymer is far larger than that of the poly (melamine) particles prepared by an electrochemical polymerization method (about several nanometers to hundreds of nanometers).
2. PME (permanent magnet Ejection) 1 Infrared spectroscopy (FTIR) analysis was performed with monomer MA and the results are shown in FIG. 3.
As can be seen from the IR spectrum analysis of the monomer MA, 3468cm -1 And 3417cm -1 The absorption peak at which corresponds to the asymmetric stretching vibration of N-H3126 cm -1 The absorption peak at the position corresponds to symmetrical stretching vibration of N-H, 1648cm -1 The absorption peak at which corresponds to flexural vibration of N-H, 1027cm -1 The absorption peak at this point corresponds to the torsional vibration of N-H, and the evidence above indicates the presence of a pronounced primary amino group (-NH) in monomer MA 2 )。1543cm -1 、1466cm -1 And 1431cm -1 The absorption peak at the position shows that obvious annular stretching vibration and semicircular stretching vibration exist in the MA monomer. 1196cm -1 The absorption peak at the position is the stretching vibration of the C-N bond. From polymelamine PME 1 The asymmetric stretching vibration absorption peak of the N-H bond has been observed from 3468cm in monomer MA in the infrared spectrum of (C) -1 And 3417cm -1 Respectively red shift to 3418cm -1 and 3374cm -1 Indicating a polymelamine PME 1 There is a pronounced tertiary amine structure. In addition, in MA, the position is 1027cm -1 The N-H torsional vibration at the location blue shifted to 1081cm -1 Site (PME) 1 ) The N atoms are still connected with H atoms in the polymelamine polymer chain, but the N-H torsional vibration frequency is improved to a certain extent due to the change of the structural arrangement of the atoms after polymerization. The above results indicate that the polymerization of monomer MA successfully occurred to yield polymer PME.
3. Monomer MA and PolyMelamine PME by X-ray photoelectron Spectrometry (XPS) 1 Is analyzed. Monomers MA and PME 1 The XPS profile of (2) is shown in FIG. 4.
As can be seen from XPS patterns, MA and PME 1 Characteristic peaks of C1s (-287.7 eV), N1s (399.0 eV) and O1s (531.9 eV) are all visible in XPS spectrum. Notably, in the PME 1 Characteristic peaks of S2 p (168.8 eV) and S2S (232.2 eV) are also present in XPS full spectrum of MA, while characteristic peaks of sulfur element are not present in XPS full spectrum of MA. The results indicate that in PME 1 The sulfur element was significantly introduced into the sample because ammonium persulfate after initiation of MA polymerization, the oxidizer residue (SO-containing 4 2- and HSO 4 - ) Is introduced into the polymelamine polymer chain.
4. In the N1s high resolution XPS spectrum of monomer MA (fig. 5), two peaks were observed, 398.5eV and 399.3eV, corresponding to the nitrogen atom in the pyridine ring (c=n, 43.5%) and the nitrogen atom in the primary amine (-NH), respectively 2 56.5%). And in the poly-melamine PME 1 In the N1s high resolution XPS spectrum (fig. 6), three peaks of 398.7eV,399.6eV and 400.7eV are observed, corresponding to the nitrogen atom in the pyridine ring (c=n, 5.7%), the nitrogen atom in the secondary amine (-NH-, 70.0%) and the polarized nitrogen atom in which delocalization occurs (-NH), respectively. + 24.3%). In PME 1 In the N1s high-resolution XPS spectrum, the occurrence of 400.7eV peak splitting also proves the formation of the polymelamine structure, which shows that the oxidation polymerization of monomer MA can be realized by taking APS as an oxidant, and the polymelamine is successfully prepared.
5. Adopts hydrogen spectrum nuclear magnetic resonance 1 H NMR，DMSO-d 6 ) Characterization of monomer MA and polymelamine PME 1 Is a chemical structure of (a). Monomer MA, oxidizer APS and Polymer PME 1 A kind of electronic device 1 The H NMR spectrum is shown in FIG. 7. H at 3.4ppm and 2.5ppm in FIG. 7 d And H e Proton signals are derived from water molecules in the sample and DMSO in the test solvent, respectively.
As can be seen from FIG. 7, in the spectrum of monomer MA, only protons H having a chemical shift of 6.0ppm were observed c The proton signal is attributed to the proton (-NH) in the primary melamine amine 2 ) While in the polymer PME 1 A kind of electronic device 1 In the H NMR spectrum, a chemical shift of 7.6ppm (H b ) And 11.0ppm (H) a ) Is assigned to-NH-and-NH respectively. + -protons in the group. And originally located at 6.0ppm of-NH in MA monomer 2 Proton signal in polymer PME 1 A kind of electronic device 1 The complete disappearance of the H NMR spectrum strongly demonstrates the successful oxidative polymerization of the melamine monomer, -NH on the melamine monomer 2 Converted to-NH-and-NH. + -structure, and no melamine monomer residues in the polymer. 1 The results of the H NMR analysis and XPS analysis mutually prove that the fact that the monomer MA is oxidatively polymerized is more strongly demonstrated.
6. Monomer MA with Polymer PME 1 Thermogravimetric analysis (TGA) was performed and the results are shown in fig. 8.
As can be seen from fig. 8, a significant weight loss of monomer MA occurs when heated to a temperature in the range of 250 to 345 c, because significant sublimation of monomer MA occurs in this temperature range, and monomer MA remains substantially free when the temperature is higher than 345 c. However, polymeric PMEs 1 The thermogravimetric analysis of (c) shows three different weight loss stages in the same temperature range, 250-350 ℃,350-500 ℃ and 500-700 ℃, respectively, which are caused by the breaking of the following three different covalent bonds: NH-NH, C-N and c=n, TGA results indicate that the polymer PME is compared to monomer MA 1 Has more excellent thermal stability, and polymer PME 1 New covalent bonds have been formed (as shown in figure 1) linking the monomers to each other. The TGA results also strongly demonstrate that monomer MA successfully undergoes oxidative polymerization to form polymelamines.
7. The products PME prepared in examples 2 to 9 were each prepared 2 、PME 3 、PME 4 、PME 5 、PME 6 、PME 7 、PME 8 、PME 9 Thermogravimetric analysis (TGA) was performed and the results are shown in figures 9 to 16, respectively.
The results show that the polymer PME 2 ～PME 9 The thermogravimetric analysis of (C) shows three different weight loss stages, namely 235-350 ℃,350-480 ℃ and 480-700 ℃ in the same temperature rangeThe weight loss stage is caused by the following three different covalent bond breaks: NH-NH, C-N and c=n. The polymerization of monomer MA successfully produced by the present invention gives a polymelamine, and the resulting polymer PME has more excellent thermal stability, and the result is the same as that of the polymer PME 1 Similarly.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (9)
1. The preparation method of the low-cost and high-purity polymelamine is characterized by comprising the following steps of:
1) Placing melamine into phytic acid for ultrasonic treatment until a uniform transparent solution, namely solution A, is formed; dissolving ammonium persulfate in deionized water to obtain a solution B; then respectively immersing the solution A and the solution B into constant-temperature water baths with the same temperature;
2) And (3) under the condition of constant-temperature water bath, introducing inactive gas into the solution A, slowly dripping the solution B into the solution A, fully stirring the obtained mixed solution for reaction, filtering and collecting a solid product after the reaction is finished, washing the solid product with deionized water for a plurality of times until the pH value of a washing solution is 7, and preserving the washing solution after freeze-drying to obtain the polymelamine.
2. The method for preparing low-cost and high-purity polymelamine according to claim 1, wherein the concentration of melamine in the solution a in the step 1) is 0.18-0.49 mol/L; the concentration of persulfate in the solution B in the step 2) is 1.29-3.39 mol/L.
3. The method for preparing the low-cost and high-purity polymelamine according to claim 1, wherein the temperature of the constant-temperature water bath in the step 1) is 0-40 ℃ and the immersion time is 20-40 min.
4. The method for preparing the low-cost and high-purity polymelamine according to claim 1, wherein the molar ratio of persulfate to melamine in the mixed solution is 3-4: 1.
5. the process for the preparation of low-cost, high-purity polymelamine as claimed in claim 1, wherein the inert gas is nitrogen, argon or helium; the inlet time of the inactive gas is 10-15 min.
6. The method for preparing the low-cost and high-purity polymelamine as claimed in claim 1, wherein the dropping speed is 0.5 to 2 drops/second.
7. The method for preparing the low-cost and high-purity polymelamine as claimed in claim 1, wherein the stirring reaction time is 20-40 min.
8. A polymelamine prepared according to the process of any one of claims 1 to 7.
9. Use of the polymelamine as claimed in claim 8 for electrical devices or biosensing.
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