CN112661941B - Method for preparing water-based polymer with assistance of diamond micropowder - Google Patents
Method for preparing water-based polymer with assistance of diamond micropowder Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 62
- 239000010432 diamond Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 33
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 9
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
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- 239000000047 product Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 8
- 229920000554 ionomer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 239000004815 dispersion polymer Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 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 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a water-based polymer with the assistance of diamond micropowder, wherein the diamond micropowder is used in the polymerization process, a mutually isolated microreaction pond is formed by utilizing gaps among the micropowder, gel is limited in a tiny area, fine polymer particles can be obtained, the polymer particles are stable and do not precipitate in water, the physical and chemical properties of the polymer are not influenced, and the problem that the conductivity of the material is damaged when a large block of material is mechanically crushed in the traditional process is solved; the added diamond micropowder can be recycled, has no pollution, and has economic benefit and environmental protection.
Description
Technical Field
The invention relates to the technical field of organic chemical industry and high polymer materials, in particular to a water-based polymer, and especially relates to a method for preparing the water-based polymer with the assistance of diamond micropowder.
Background
The aqueous polymer containing thiophene, aniline and pyrrole structures is an emerging semiconductor, has high conductivity, nonlinear optical property, electroluminescent property and electrochromic property, and has good flexibility, low cost and great application value in the aspects of military industry and civil use.
The basic structure of the catalyst has a long large pi bond conjugated structure, electrons can be lost under the action of an oxidant, cations dispersed on a plurality of conjugated units are formed, and the cationic conjugated structure has good electron conduction performance. Conjugated polymers in the cationic state require anions to complex stabilization, a process known as "doping", typically using acidic ionomers such as: poly-4-vinylbenzenesulfonic acid, polyvinylsulfonic acid, and copolymers thereof, having the general chemical formula:
the choice of polymer anions has two advantages: the anionic polymer and the cationic polymer are mutually entangled, and the acidic ionomer is not only a doping agent but also a cross-linking agent, so that the material has good durability; meanwhile, the anionic polymer has good water solubility, and can wrap the cationic conjugated polymer to disperse in water to prepare the aqueous coating, so that the aqueous coating is more environment-friendly. The synthetic process is, for example, to polymerize monomers containing thiophene structures in aqueous poly-4-vinylbenzenesulfonic acid by persulfate oxidation, and the polymer forms a cationic state under the action of an oxidant and intertwines with an anionic state polymer to form a colloidal particle polymerization product. After the reaction, the inorganic salts produced by the chemical oxidation are removed by ion exchange and dispersed to form an aqueous dispersion of polymer particles, as described in Bayer company patents EP0339340 and EP 0440957.
The reaction is characterized in that polymerization and crosslinking occur simultaneously, a polymerization system in the reaction is difficult to disperse effectively, a product is directly formed into nano-scale fine particles, the polymerization reaction is sensitive to an emulsifier, the emulsifier is not inert in the reaction, the emulsifier participates in the reaction, the purity of the product is reduced, and the product cannot be purified, so that the reaction is difficult to disperse by emulsion polymerization. The traditional process is to obtain a coarse-grained hydrocolloid dispersion, and then break the large grains into nanometer-scale small grains by a mechanical shearing method with a high-pressure nanometer homogenizer, as described in patent CN1839448A of the company of the aka. Mechanical shearing pulls the cross-linking points formed by anions and cations between the two polymers in the large particles, and breaks the cross-linking points into small particles, but the conductivity of the material is reduced due to the fact that the cross-linking points are doping points at the same time, and the doping points are damaged. After the doped points at the edges of the particles are pulled apart, the conductive high molecular polymer chains shrink inwards the particles, the acidic ionomer is hydrophilic and stretches towards the water phase, the movement directions of the two polymers on the interface are opposite, the original doped points are irreversibly broken, and the conductivity is permanently reduced. Meanwhile, the particles can generate larger deformation in the shearing process, doping points inside the particles can be distorted and misplaced to be destroyed, and the destruction cannot be completely recovered after the shearing is completed due to the steric effect.
In summary, the result of shear fracture is a drop in conductivity of more than a factor of 10. More usage and greater film thickness will be required to achieve the same conductivity after the conductivity is reduced, which increases cost and reduces transparency, losing its own advantages.
Therefore, it is desirable to find a way to disperse directly into nanoparticles while polymerizing while bypassing mechanical disruption.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing a water-based polymer with the assistance of diamond micro powder.
In order to achieve the above purpose, the technical scheme of the method for preparing the water-based polymer with the assistance of the diamond micro powder provided by the invention is as follows:
the method comprises the following steps: and adding diamond micropowder in the process of preparing the water-based polymer, forming a micro-reaction tank in gaps among the diamond micropowder, and limiting gel in the micro-reaction tank to obtain the stable water-based polymer.
Preferably, the diamond micropowder, water and the reaction raw material are simultaneously added into the reaction vessel, and slurry is formed in the reaction vessel, and the reaction is carried out while stirring.
Preferably, the rotation speed during stirring is more than 50 revolutions per minute.
Preferably, after the aqueous polymerization reaction is completed, the aqueous polymer and the diamond micropowder are separated by means of extraction by adding water.
Preferably, the preparation of the aqueous polymer is carried out at a temperature of 2℃to 40 ℃.
Preferably, the grain size of the diamond micro powder ranges from 0.1 micrometers to 20 micrometers.
Preferably, the impurity content of the diamond micropowder is less than one percent.
Preferably, the aqueous polymer is formed by combining a polymer and a cross-linking agent, wherein the polymer is polyaniline, polypyrrole or poly 3, 4-ethylene dioxythiophene; the cross-linking agent is poly-4-vinylbenzene sulfonic acid, polyvinyl sulfonic acid, salts formed by the polyvinyl sulfonic acid and alkali metal or alkaline earth metal, and copolymers thereof.
Preferably, the solvent used in the process of preparing the aqueous polymer is water or a mixed solvent of water and an organic solvent.
According to the method for preparing the water-based polymer with the assistance of the diamond micro powder, the diamond micro powder is used in the polymerization process, gaps among the micro powder are utilized to form micro reaction tanks which are isolated from each other, gel is limited in a micro area, fine polymer particles can be obtained, the polymer particles are stable in water and do not precipitate, the physical and chemical properties of the polymer are not affected, and the problem that the conductivity of the material is damaged when a large block of material is mechanically crushed in the traditional process is solved; the added diamond micropowder can be recycled, has no pollution, and has economic benefit and environmental protection.
Detailed Description
In order to more clearly describe the technical contents of the present invention, a further description will be made below in connection with specific embodiments.
The method for preparing the water-based polymer with the assistance of the diamond micro powder is mainly characterized in that the diamond micro powder is added in the process of preparing the water-based polymer, a micro reaction tank is formed by utilizing gaps among the diamond micro powder, gel is limited in the micro reaction tank, and fine polymer particles which are stably dispersed in water are obtained.
The water-based polymer is formed by combining a polymer and a cross-linking agent, wherein the polymer is polyaniline, polypyrrole or poly-3, 4-ethylenedioxythiophene; the cross-linking agent is water-soluble acidic ionomer containing sulfonic acid groups or salt formed by the acidic ionomer and alkali metal or alkaline earth metal, and concretely, the acidic ionomer containing sulfonic acid groups is poly-4-vinylbenzenesulfonic acid, polyvinylsulfonic acid or copolymer between the two.
Adding diamond powder, water and reaction raw materials into a reaction container at the same time, forming slurry in the reaction container, reacting while stirring, and separating the water-based polymer from the diamond powder by adding water for extraction after the reaction is finished; finally, purifying the aqueous solution of the polymer and concentrating to the required concentration; the diamond powder is used for the next reaction after being washed with water.
The solvent used in the process of preparing the aqueous polymer is water or a mixed solvent of water and an organic solvent, and the less the solvent is, the better the solvent is under the premise of being capable of stirring; the reaction temperature is 2-40 ℃, and the reaction temperature can be actually adjusted according to the actual reaction, wherein the particles with lower temperature are finer; the stirring speed is higher, the particles of the polymerized product are smaller, the rotating speed is usually more than 50 revolutions per minute, the stirring effect and the rotating speed are related to the size and the shape of the stirring paddles, and if the stirring paddles are large, the rotating speed can be slower, and the rotating speed can be adjusted according to the actual stirring effect.
In the process provided by the present invention, the inventors utilized very fine solid powders that have a similar segregation effect as the emulsifier. The water can be separated into small chambers surrounded by the outer walls of the solid particles by adding sufficient solid micropowder to the reaction solution to cause the water to become a dispersed phase. The small chambers are not completely isolated, water, acid ionomer and small molecular monomer can permeate between the small chambers under the action of stirring, so that the mass and heat transfer conditions required by the reaction are met, but the particles of the polymerization product reaching a certain size are closed in the small chambers formed by the outer walls of the powder due to the increase of the volume and the decrease of the fluidity of the particles. This allows the particle size of the polymer product to be controlled by the size of the solid particles and the dispersion during agitation.
In addition, solid powder is used for overcoming gelation of aqueous polymer, and there is no clear research record, mainly because as the solid powder is thinned, the surface effect is larger and is different from the macroscopic property of the body, the microscopic morphology and molecular structure of the surface interface have complex influence on adsorption, desorption and chemical activity of various components in the reaction, and the technical problem is lack of rules for maturation and circulation.
The inventors have found during the development that most solid powders cannot be used in the aqueous polymer of the present invention, for example, aqueous polymerization is carried out in a strongly acidic environment, in which powders such as alumina, zirconia and the like react, and cannot be used; while silicon oxide and silicon nitride powder have small influence on the reaction, the adsorption of the silicon oxide and silicon nitride powder on the product is large, and the product is difficult to purify; glass frit can decrease the electrical conductivity of the product; the reaction hardly proceeds in mica powder or talc powder. Organic polymer powders, such as polystyrene microspheres, polymethyl methacrylate microspheres, are soluble in aniline, pyrrole, 3, 4-ethylenedioxythiophene, absorb a portion of the reaction monomers into the powder while excluding hydrophilic acidic ionomers from the powder, making the reaction impossible to proceed in normal proportions, and the adsorption of the product is large, making the product difficult to purify.
Through screening and verification, the inventor uses diamond micro powder to assist the water-based polymerization reaction, diamond is a crystal formed by elemental carbon in a regular triangular pyramid configuration, wherein each carbon atom forms a covalent bond with the other four carbon atoms through an SP3 hybridization orbit, and the bond is completely nonpolar, has no free electrons, shows no electrostatic attraction to external atoms and has stable chemical properties due to the fact that electronegativity of bonding atoms is the same; it does not react with acid and alkali, and does not react with oxidant or reducer at normal temperature, and presents chemical inertia; the surface adsorptivity is low, the adsorption effect on the reaction raw materials is weak, and the polymerization reaction is not influenced; has hydrophobicity, is not adhered with hydrophilic polymerization products, and is easy to be separated. The grain size of the diamond micropowder can be in the range of 0.1-20 microns and can be selected according to the needs. The purity of the diamond powder is used as an optimized condition, the higher the purity is, the better the use effect is, and the four-type material is generally required, and the impurity content of the diamond micro powder is lower than one percent.
Example 1
113 g of high-purity diamond powder having a particle diameter of about 0.2 to 0.3 μm was charged into the flask, and 48.5 g of an aqueous solution of poly-4-vinylbenzenesulfonic acid having a concentration of 1.03% was added into the flask and stirred uniformly. Then 0.20 g of 3, 4-ethylenedioxythiophene is added under the protection of nitrogen and stirred uniformly. 0.5 g of sodium persulfate and 0.0035 g of ferric sulfate dissolved in 2.8 g of water were added to the reaction system, and the mixture was stirred at a speed of 200 rpm and reacted at 25℃for 24 hours. After the reaction was completed, 50 g of water was added while stirring, and after the stirring was stopped, the diamond powder was precipitated, and the supernatant was collected. Then 50 g of water is added into the diamond powder precipitate to stir and wash, and the supernatant is taken after stopping stirring. The washing process was repeated 4 times. The supernatants were combined, the supernatants were filtered after 8 hours of exchange with 2.65 g of anion exchange resin, and the supernatants were filtered after 8 hours of exchange with 8.35 g of cation exchange resin. Finally, the filtrate was concentrated to 1.2%.
The aqueous polymer dispersion was allowed to stand for 3 years without precipitation. The coating film is not cracked and peeled off, and the surface sheet resistance is 100 ohms under the condition of 70% transparency.
Comparative example 1
48.5 g of an aqueous solution of poly-4-vinylbenzenesulfonic acid having a concentration of 1.03% was added to the flask and stirred well. Then 0.20 g of 3, 4-ethylenedioxythiophene is added under the protection of nitrogen and stirred uniformly. 0.5 g of sodium persulfate and 0.0035 g of ferric sulfate dissolved in 2.8 g of water were added to the reaction system, and the mixture was stirred at a speed of 200 rpm and reacted at 25℃for 24 hours. After the completion of the reaction, 2.65 g of the anion exchange resin was used for 8 hours, the supernatant was filtered, and 8.35 g of the cation exchange resin was used for 8 hours, and the supernatant was filtered. Finally, the filtrate was concentrated to 1.2%.
The polymer aqueous dispersion is totally precipitated after standing for 1 week, and the coating film is cracked and easily peeled off. Crushing to nanometer level with a high pressure nanometer homogenizer at 1500 bar, and at a transparency of 70%, the surface sheet resistance is 5000 ohm.
Example 2
128 g of high-purity diamond powder having a particle size of about 0.8 to 1 μm was charged into the flask, and 51.44 g of an aqueous solution of poly-4-vinylbenzenesulfonic acid having a concentration of 2.8% was added into the flask and stirred uniformly. Then 0.51 g of aniline is added and stirred well. Stirring was carried out at a speed of 200 rpm at 6 ℃. 0.74 g of ammonium persulfate was dissolved in 2 g of water, and added dropwise to the reaction system over 2 hours, followed by further reaction for 4 hours. After the reaction was completed, 50 g of water was added while stirring, and the diamond powder was precipitated, and the supernatant was collected. Then 50 g of water is added into the diamond powder precipitate to stir and wash, and the supernatant is taken after stopping stirring. The washing process was repeated 4 times. The supernatants were combined and exchanged with 4.09 g of anion exchange resin for 8 hours, the supernatants were filtered off, and 12.89 g of cation exchange resin for 8 hours, the supernatants were filtered off. Finally, the filtrate was concentrated to 1.2%.
The aqueous polymer dispersion was dried to a constant weight at 50℃and ground to a powder, which was pressed into a wafer of a certain thickness by a tablet press under a pressure of 10MPa, and the conductivity was measured by a four-probe method. The conductivity was 51S/cm. The aqueous polymer dispersion has no sediment after standing for 3 years, and the coating film is not cracked or peeled off.
Example 3
127 grams of high purity diamond powder having a particle size of about 0.4 to 0.5 microns was added to the flask, 1.43 grams of sodium poly-4-vinylbenzenesulfonate was dissolved in 50 grams of deionized water, and the flask was added and stirred well. Then 0.24 g pyrrole was added and stirred well. Stirring was carried out at a speed of 100 rpm at 5 ℃. Ammonium persulfate 1.23 g was dissolved in 3 g of water, and was added dropwise to the reaction system over 1 hour, followed by further reaction for 10 hours. After the reaction was completed, 50 g of water was added while stirring, and after the stirring was stopped, the diamond powder was precipitated, and the supernatant was collected. Then 50 g of water is added into the diamond powder precipitate to stir and wash, and the supernatant is taken after stopping stirring. The washing process was repeated 4 times. The supernatants were combined, the supernatants were filtered after 8 hours of exchange with 6.8 g of anion exchange resin, and the supernatants were filtered after 8 hours of exchange with 21.43 g of cation exchange resin. Finally, the filtrate was concentrated to 1.2%.
The aqueous polymer solution was dried to a constant weight at 50 ℃, ground into powder, pressed into a disc of a certain thickness by a tablet press under a pressure of 10MPa, and its conductivity was measured by a four-probe method. The conductivity was 12S/cm. The aqueous polymer dispersion has no sediment after standing for 3 years, and the coating film is not cracked or peeled off.
Example 4
127 grams of high purity diamond powder having a particle size of about 0.2 to 0.3 microns was added to the flask, and 51.28 grams of 2.5% strength aqueous solution of poly-4-vinylbenzenesulfonic acid in a mixed solvent of acetonitrile and deionized water at a 1:9 (volume ratio) solvent was added to the flask. Then 0.24 g pyrrole was added and stirred well. Stirring was carried out at a speed of 50 rpm at 5 ℃. Ammonium persulfate 1.23 g was dissolved in 3 g of water, and was added dropwise to the reaction system over 1 hour, followed by further reaction for 10 hours. After the reaction was completed, 50 g of water was added while stirring, and after the stirring was stopped, the diamond powder was precipitated, and the supernatant was collected. Then 50 g of water is added into the diamond powder precipitate to stir and wash, and the supernatant is taken after stopping stirring. The washing process was repeated 4 times. The supernatants were combined, the supernatants were filtered after 8 hours of exchange with 6.8 g of anion exchange resin, and the supernatants were filtered after 8 hours of exchange with 21.43 g of cation exchange resin. Finally, the filtrate was concentrated to 1.2%.
The aqueous polymer solution was dried to a constant weight at 50 ℃, ground into powder, pressed into a disc of a certain thickness by a tablet press under a pressure of 10MPa, and its conductivity was measured by a four-probe method. The conductivity was 13S/cm. The aqueous polymer dispersion has no sediment after standing for 3 years, and the coating film is not cracked or peeled off.
Example 5
113 g of high-purity diamond powder having a particle diameter of about 0.2 to 0.3 μm was charged into the flask, and 48.4 g of an aqueous solution of 4-vinylbenzenesulfonic acid-vinylsulfonic acid copolymer (molar ratio 1:1) having a concentration of 0.826% was added into the flask and stirred uniformly. Then 0.20 g of 3, 4-ethylenedioxythiophene is added under the protection of nitrogen and stirred uniformly. 0.5 g of sodium persulfate and 0.0035 g of ferric sulfate dissolved in 2.8 g of water were added to the reaction system, and the mixture was stirred at a speed of 200 rpm and reacted at 25℃for 24 hours. After the reaction was completed, 50 g of water was added while stirring, and after the stirring was stopped, the diamond powder was precipitated, and the supernatant was collected. Then 50 g of water is added into the diamond powder precipitate to stir and wash, and the supernatant is taken after stopping stirring. The washing process was repeated 4 times. The supernatants were combined, the supernatants were filtered after 8 hours of exchange with 2.65 g of anion exchange resin, and the supernatants were filtered after 8 hours of exchange with 8.35 g of cation exchange resin. Finally, the filtrate was concentrated to 1.2%.
The aqueous polymer dispersion was allowed to stand for 3 years without precipitation. The coating film was free from cracking and peeling, and had a surface sheet resistance of 200 ohms at a transparency of 70%.
As is clear from examples 1 to 5 and comparative example 1, the polymer particles without adding diamond powder were coarse, and a large amount of precipitate was formed in water for 1 week, and the coating film was easily peeled off due to cracking, and the transparency was low. The conductivity is reduced by more than 10 times after being crushed by a micro-jet homogenizer, and the requirements of industrial application are not met. The product added with diamond powder for auxiliary polymerization has high conductivity and fine particles, can be stably dispersed in water for more than 3 years without precipitation and further crushing. The coating film is not cracked and peeled off, and the transparency can reach more than 85 percent.
The method for preparing the water-based polymer with the assistance of the diamond micro powder has the beneficial effects that the diamond micro powder is used for the water-based polymer which is easy to gel:
1. in the polymerization process, gaps among the micro powder are utilized to form micro reaction tanks which are isolated from each other, gel is limited in a micro area, very fine polymer particles can be obtained, the polymer particles are stable in water and do not precipitate, and the conductivity of a polymerization product is not influenced;
2. the subsequent crushing step can be omitted by diamond powder assisted polymerization, so that the production efficiency is improved;
3. the diamond powder can be recycled, so that the economic loss is not increased, and pollutant emission is not generated;
4. the artificial diamond powder is used as a common abrasive, has low price, is easy to obtain and has good economic benefit.
In this specification, the invention has been described with reference to specific embodiments thereof. It will be apparent, however, that various modifications and changes may be made without departing from the spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.
Claims (6)
1. A method for preparing an aqueous polymer with the assistance of diamond micropowder, which is characterized by comprising the following steps: adding diamond micropowder in the process of preparing the water-based polymer, forming a micro-reaction tank in gaps among the diamond micropowder, and limiting gel in the micro-reaction tank to obtain a stable water-based polymer, wherein the water-based polymer is formed by combining a polymer and a cross-linking agent, and the polymer is polyaniline, polypyrrole or poly 3, 4-ethylenedioxythiophene; the cross-linking agent is poly-4-vinylbenzene sulfonic acid, polyvinyl sulfonic acid, salts formed by the polyvinyl sulfonic acid and alkali metal or alkaline earth metal, and copolymers thereof.
2. The method for preparing an aqueous polymer assisted by diamond micropowder according to claim 1, wherein the diamond micropowder is added to the reaction vessel together with water and the reaction raw material to form a slurry in the reaction vessel, and the reaction is carried out while stirring.
3. The method for preparing the aqueous polymer assisted by the diamond micro powder according to claim 1, wherein the aqueous polymer and the diamond micro powder are separated by adding water for extraction after the aqueous polymerization reaction is completed.
4. A method for preparing an aqueous polymer assisted by diamond micropowder according to any of claims 1 to 3, wherein the diamond micropowder has a particle diameter in the range of 0.1 to 20 μm.
5. A method of preparing an aqueous polymer assisted by diamond micro powder according to any one of claims 1 to 3, wherein the impurity content of the diamond micro powder is less than one percent.
6. A method for preparing an aqueous polymer assisted by diamond micro powder according to any one of claims 1 to 3, wherein the solvent used in the preparation of the aqueous polymer is water or a mixed solvent of water and an organic solvent.
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| GB0310419D0 (en) * | 2003-05-07 | 2003-06-11 | Ciba Spec Chem Water Treat Ltd | Treatment of aqueous suspensions |
| WO2012138040A1 (en) * | 2011-04-07 | 2012-10-11 | 광주과학기술원 | Nanodiamond-polymer nanoparticle composite, and a production method therefor |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN108251058A (en) * | 2018-03-01 | 2018-07-06 | 燕山大学 | A kind of preparation method of diadust surface growth polyaniline coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0310419D0 (en) * | 2003-05-07 | 2003-06-11 | Ciba Spec Chem Water Treat Ltd | Treatment of aqueous suspensions |
| WO2012138040A1 (en) * | 2011-04-07 | 2012-10-11 | 광주과학기술원 | Nanodiamond-polymer nanoparticle composite, and a production method therefor |
| CN106810675A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of graphene composite conductive material and preparation method |
| CN108251058A (en) * | 2018-03-01 | 2018-07-06 | 燕山大学 | A kind of preparation method of diadust surface growth polyaniline coating |
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