CN112661941A - 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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- CN112661941A CN112661941A CN202011417615.6A CN202011417615A CN112661941A CN 112661941 A CN112661941 A CN 112661941A CN 202011417615 A CN202011417615 A CN 202011417615A CN 112661941 A CN112661941 A CN 112661941A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 63
- 239000010432 diamond Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 29
- 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 12
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 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
- 239000000126 substance Substances 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920000554 ionomer Polymers 0.000 description 8
- 239000004815 dispersion polymer Substances 0.000 description 7
- 239000002244 precipitate Substances 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
- 239000003729 cation exchange resin Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001450 anions Chemical class 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
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000000227 grinding Methods 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
- 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
- 238000003825 pressing Methods 0.000 description 3
- 239000000523 sample 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 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
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 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
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012686 granular polymerization Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000638 solvent extraction Methods 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
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a method for preparing a water-based polymer with the assistance of diamond micropowder, which uses the diamond micropowder in the polymerization process, forms a micro-reaction tank which is isolated from each other by utilizing the clearance between the micropowder, limits gel in a tiny area, can obtain fine polymer particles, is stable in water without precipitation, does not influence the physical and chemical properties of the polymer, and overcomes the problem that the conductivity of a material is damaged when a large material is mechanically crushed in the traditional process; 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 molecular materials, in particular to a water-based polymer, and particularly relates to a method for preparing the water-based polymer by diamond micro powder in an auxiliary manner.
Background
The aqueous polymer containing thiophene, aniline and pyrrole structures is a new type of semiconductor, has high conductivity, nonlinear optical property, electroluminescent property and electrochromic property, is good in flexibility and low in cost, and has great application value in military industry and civil use.
The basic structure of the material has a long large pi bond conjugated structure, and the material can lose electrons under the action of an oxidant to form cations dispersed on a plurality of conjugated units, and the conjugated structure in a cation state has good electron conduction performance. Conjugated polymers in the cationic state require anions for complexing stabilization, a process known as "doping", and typically use acidic ionomers such as: poly 4-vinylbenzenesulfonic acid, polyvinylsulfonic acid and copolymers therebetween, having the general chemical formula:
the choice of polymer anion 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 crosslinking agent, so that the material is good in durability; meanwhile, the anionic polymer has good water solubility, can wrap the cationic conjugated polymer and disperse in water to prepare the aqueous coating, and is more environment-friendly. The synthesis process is that for example, in the aqueous solution of poly 4-vinyl benzene sulfonic acid, the monomer containing thiophene structure is oxidized and polymerized by persulfate, the polymer forms a cation state under the action of oxidant, and the cation state and the anion state polymer are mutually entangled to form a colloid granular polymerization product. After the reaction, inorganic salts produced by chemical oxidation are removed by ion exchange, and then dispersed to form an aqueous dispersion of polymer particles, as described in bayer patents EP0339340 and EP 0440957.
The reaction is characterized in that polymerization and crosslinking occur simultaneously, the polymerization system in the reaction is difficult to be effectively dispersed, so that the product directly forms nano-scale fine particles, and the polymerization reaction is sensitive to an emulsifier, the emulsifier is not inert in the reaction and can participate in the reaction, so that the purity of the product is reduced and the product cannot be purified, and the reaction is difficult to be dispersed by emulsion polymerization. The traditional process is to obtain aqueous colloidal dispersion of coarse particles, and then break the large particles into nanometer-sized small particles by mechanical shearing with a high-pressure nanometer homogenizer, as described in Ack-Co patent CN 1839448A. The cross-linking points formed by anions and cations between two polymers in a large particle are pulled apart by mechanical shearing to be broken into small particles, but the cross-linking points are also doping points, so that the conductivity of the material is reduced by destroying the doping points. After the doped points at the edges of the particles are pulled apart, the original doped points are irreversibly destroyed and the conductivity is permanently reduced because the conductive high molecular polymer chains are hydrophobic and shrink into the particles, and the acidic ionomer is hydrophilic and stretches towards the water phase, and the moving directions of the two polymers on the interface are opposite. Meanwhile, the particles can generate large deformation in the shearing process, doping points in the particles can be distorted and dislocated to be damaged, and the damage cannot be completely recovered after the shearing is finished due to the steric effect.
In summary, the shear fracture results in a 10-fold or greater decrease in conductivity. The decrease in conductivity will require more amount and greater film thickness to achieve the same conductive effect, which increases cost and decreases transparency, losing its advantages.
Therefore, there is a need to find a method for directly dispersing 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 purpose, the technical scheme of the method for preparing the water-based polymer by the aid of the diamond micro powder is as follows:
the method comprises the following steps: adding diamond micro powder in the process of preparing the water-based polymer, forming a micro-reaction tank by gaps among the diamond micro powder, and limiting gel in the micro-reaction tank to obtain the stable water-based polymer.
Preferably, the diamond fine powder is added to the reaction vessel together with water and the reaction material, and the reaction is carried out while stirring the mixture to form a slurry in the reaction vessel.
Preferably, the rotation speed during stirring is more than 50 revolutions per minute.
Preferably, after the aqueous polymerization reaction is finished, the aqueous polymer and the diamond micropowder are separated by adding water for extraction.
Preferably, the preparation of the aqueous polymer is carried out at 2 ℃ to 40 ℃.
Preferably, the particle size range of the diamond micro powder is 0.1-20 microns.
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-ethylenedioxythiophene; the cross-linking agent is poly 4-vinyl benzene sulfonic acid, polyvinyl sulfonic acid, salt formed by the poly 4-vinyl benzene sulfonic acid and the polyvinyl sulfonic acid with alkali metal or alkaline earth metal, and copolymer 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 micropowder, the diamond micropowder is used in the polymerization process, the micro reaction tanks which are isolated from each other are formed by utilizing gaps among the micropowder, the 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 a large material is damaged while the large 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, the following further description is given in conjunction with specific embodiments.
The method for preparing the water-based polymer with the assistance of the diamond micro powder mainly comprises the steps of adding the diamond micro powder in the process of preparing the water-based polymer, forming a micro reaction tank by utilizing gaps among the diamond micro powder, and limiting gel in the micro reaction tank to obtain fine polymer particles which are stably dispersed in water.
The aqueous polymer is formed by combining a polymer and a cross-linking agent, wherein the polymer is polyaniline, polypyrrole or poly 3, 4-ethylenedioxythiophene; the crosslinking agent is an acidic ionomer which contains sulfonic acid groups and can be dissolved in water, or a salt of the acidic ionomer and alkali metal or alkaline earth metal, and specifically, the acidic ionomer containing the sulfonic acid groups is poly-4-vinyl benzene sulfonic acid, polyvinyl sulfonic acid or a copolymer of the two.
Adding diamond powder, water and reaction raw materials into a reaction container at the same time, forming slurry in the reaction container, stirring and reacting at the same time, and separating the water-based polymer from the diamond powder in a water-adding extraction mode after the reaction is finished; finally, purifying the aqueous solution of the polymer, and concentrating to the required concentration; the diamond powder can be used for the next reaction after being washed by water.
The solvent used in the process of preparing the waterborne polymer is water or a mixed solvent of water and an organic solvent, and the less the solvent, the better the solvent is on the premise of stirring; the reaction temperature is 2-40 ℃, the particles can be a little finer at a lower temperature, and the reaction temperature can be adjusted according to the actual reaction; the stirring speed is faster, the particle size of the polymerization product is smaller, the rotating speed is usually more than 50 rpm, the stirring effect and the rotating speed are related to the size and the shape of the stirring paddle, if the stirring paddle is larger, 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 morphologically have a similar partitioning effect as the emulsifier. If sufficient solid fine powder is added to the reaction solution to make water into a dispersed phase, the water can be separated in a small chamber surrounded by the outer wall of the solid particles. The small chambers are not completely isolated, water, acid ionomer and small molecular monomer can permeate among the small chambers under the action of stirring to meet the mass and heat transfer conditions required by the reaction, but the polymerization product particles reaching a certain size are sealed in the small chambers formed by the outer walls of the powder due to the increase of the volume and the reduction of the fluidity of the polymerization product particles. This allows the size of the solid particles and the dispersion during stirring to be used to control the particle size of the polymer product.
In addition, the solid powder is used for overcoming the gelation of the aqueous polymer, and no clear research is recorded, mainly because the surface effect is larger and larger along with the thinning of the solid powder and is different from the macroscopic property of the bulk, the micro-morphology and the molecular structure of the surface interface have complicated influence on the adsorption and desorption of various components in the reaction and the chemical activity thereof, and the technical problem is lack of a mature and recyclable rule.
The inventors found in the course of development that most of the solid powders cannot be used for the aqueous polymer of the present invention, for example, the aqueous polymerization reaction is carried out in a strongly acidic environment, and powders of alumina, zirconia, etc. react therein and cannot be used; although the silicon oxide powder and the silicon nitride powder have small influence on the reaction, the adsorption on the product is large, and the product is difficult to purify; the glass powder can reduce the conductivity of the product; the reaction hardly proceeds in mica powder and talcum powder. Organic polymer powder, for example, polystyrene microspheres and polymethyl methacrylate microspheres can be dissolved in aniline, pyrrole and 3, 4-ethylenedioxythiophene, can absorb a part of reaction monomers to enter the powder, and can exclude hydrophilic acidic ionomer from the powder, so that the reaction cannot be carried out at a normal ratio, the adsorption on the product is large, and the product is difficult to purify.
The inventor is screened and verified that diamond micropowder is used for assisting aqueous polymerization reaction, the diamond is a crystal formed by simple substance carbon in a regular triangular pyramid configuration, each carbon atom forms a covalent bond with other four carbon atoms through an SP3 hybridization orbit, and the bond is completely nonpolar and has no free electrons due to the same electronegativity of bonding atoms, shows no electrostatic attraction to external atoms and has stable chemical properties; it does not react with acid and alkali, does not react with oxidant or reducing agent at normal temperature, and presents chemical inertia; the surface adsorbability is low, the adsorption effect on reaction raw materials is weak, and the polymerization reaction is not influenced; has hydrophobic property, and is not adhered to hydrophilic polymer product and is easy to separate. The grain size range of the diamond micro powder can be 0.1-20 microns and can be selected according to requirements. The purity of the diamond powder is taken as an optimized condition, the higher the purity is, the better the use effect is, four types of materials are generally required, and the impurity content of the diamond micro powder is less than one percent.
Example 1
113 g of high purity diamond powder having a particle size of about 0.2 to 0.3 μm was charged into the flask, and 48.5 g of a 1.03% aqueous solution of poly 4-vinylbenzenesulfonic acid was added to 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 are dissolved in 2.8 g of water, added into the reaction system, stirred at the rotating speed of 200 r/min and reacted for 24 hours at the temperature of 25 ℃. After the reaction, 50 g of water was added while stirring, and after the stirring was stopped, diamond powder was precipitated to obtain a supernatant. Then 50 g of water is added into the diamond powder precipitate, the mixture is stirred and washed, and the supernatant is taken after the stirring is stopped. The washing process was repeated 4 times. The supernatants were combined, exchanged for 8 hours with 2.65 g of anion exchange resin and filtered, and then exchanged for 8 hours with 8.35 g of cation exchange resin and filtered. The filtrate was finally concentrated to 1.2%.
The aqueous polymer dispersion was left standing for 3 years without precipitation. The coating film does not crack and peel off, and the surface square resistance is 100 ohms under the condition of 70 percent of transparency.
Comparative example 1
48.5 g of a 1.03% aqueous solution of poly-4-vinylbenzenesulfonic acid was added to the flask, and the mixture was stirred. 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 are dissolved in 2.8 g of water, added into the reaction system, stirred at the rotating speed of 200 r/min and reacted for 24 hours at the temperature of 25 ℃. After the reaction was completed, the supernatant was filtered after exchanging with 2.65 g of anion exchange resin for 8 hours, and the supernatant was filtered after exchanging with 8.35 g of cation exchange resin for 8 hours. The filtrate was finally concentrated to 1.2%.
The aqueous polymer dispersion was allowed to stand for 1 week, and then, the polymer dispersion was precipitated completely, and the coating film was cracked and easily peeled off. Crushing to nanometer level with high pressure nanometer homogenizer at 1500 bar pressure, and surface square resistance of 5000 ohm under transparency of 70%.
Example 2
128 g of high-purity diamond powder having a particle size of about 0.8 to 1 μm was put into the flask, 51.44 g of a 2.8% aqueous solution of poly-4-vinylbenzenesulfonic acid was added into the flask, and the mixture was stirred uniformly. Then 0.51 g aniline was added and stirred well. Stirring was carried out at 6 ℃ and 200 rpm. 0.74 g of ammonium persulfate was dissolved in 2 g of water, and the solution was added dropwise to the reaction system over 2 hours, followed by further reaction for 4 hours. After the reaction, 50 g of water was added under stirring, and the diamond powder was precipitated to obtain a supernatant. Then 50 g of water is added into the diamond powder precipitate, the mixture is stirred and washed, and the supernatant is taken after the stirring is stopped. The washing process was repeated 4 times. The supernatants were combined and exchanged with 4.09 g of anion exchange resin for 8 hours and then filtered, and then exchanged with 12.89 g of cation exchange resin for 8 hours and then filtered. The filtrate was finally concentrated to 1.2%.
Drying the polymer aqueous dispersion at 50 ℃ to constant weight, grinding into powder, pressing into a wafer with a certain thickness by a tablet machine under the pressure of 10MPa, and measuring the electric conductivity by a four-probe method. The conductivity was 51S/cm. The aqueous polymer dispersion is free from precipitation after standing for 3 years, and a coating film is free from cracking and peeling.
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, and 1.43 grams of sodium poly-4-vinylbenzenesulfonate was dissolved in 50 grams of deionized water and added to the flask and stirred well. Then 0.24 g of pyrrole is added and stirred evenly. Stirring was carried out at 5 ℃ and at a rotational speed of 100 rpm. Ammonium persulfate 1.23 g was dissolved in water 3 g, and was added dropwise to the reaction system over 1 hour, followed by further reaction for 10 hours. After the reaction, 50 g of water was added while stirring, and after the stirring was stopped, diamond powder was precipitated to obtain a supernatant. Then 50 g of water is added into the diamond powder precipitate, the mixture is stirred and washed, and the supernatant is taken after the stirring is stopped. The washing process was repeated 4 times. The supernatants were combined, exchanged for 8 hours with 6.8 g of anion exchange resin and filtered, and then exchanged for 8 hours with 21.43 g of cation exchange resin and filtered. The filtrate was finally concentrated to 1.2%.
Drying the polymer aqueous solution at 50 ℃ to constant weight, grinding the polymer aqueous solution into powder, pressing the powder into a wafer with a certain thickness by a tablet machine under the pressure of 10MPa, and measuring the electric conductivity of the wafer by a four-probe method. The conductivity was 12S/cm. The aqueous polymer dispersion is free from precipitation after standing for 3 years, and a coating film is free from cracking and peeling.
Example 4
127 g of high purity diamond powder having a particle size of about 0.2 to 0.3 μm was charged into the flask, and 51.28 g of a 2.5% aqueous solution of poly 4-vinylbenzenesulfonic acid as a mixed solvent of acetonitrile and deionized water in a ratio of 1:9 (by volume) was added into the flask. Then 0.24 g of pyrrole is added and stirred evenly. Stirring was carried out at 5 ℃ and 50 rpm. Ammonium persulfate 1.23 g was dissolved in water 3 g, and was added dropwise to the reaction system over 1 hour, followed by further reaction for 10 hours. After the reaction, 50 g of water was added while stirring, and after the stirring was stopped, diamond powder was precipitated to obtain a supernatant. Then 50 g of water is added into the diamond powder precipitate, the mixture is stirred and washed, and the supernatant is taken after the stirring is stopped. The washing process was repeated 4 times. The supernatants were combined, exchanged for 8 hours with 6.8 g of anion exchange resin and filtered, and then exchanged for 8 hours with 21.43 g of cation exchange resin and filtered. The filtrate was finally concentrated to 1.2%.
Drying the polymer aqueous solution at 50 ℃ to constant weight, grinding the polymer aqueous solution into powder, pressing the powder into a wafer with a certain thickness by a tablet machine under the pressure of 10MPa, and measuring the electric conductivity of the wafer by a four-probe method. The conductivity was 13S/cm. The aqueous polymer dispersion is free from precipitation after standing for 3 years, and a coating film is free from cracking and peeling.
Example 5
113 g of high purity diamond powder having a particle size of about 0.2 to 0.3 μm was charged into a flask, 48.4 g of an aqueous solution of a copolymer of 4-vinylbenzenesulfonic acid and vinylsulfonic acid (molar ratio 1:1) having a concentration of 0.826% was added to the flask, and the mixture was 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 are dissolved in 2.8 g of water, added into the reaction system, stirred at the rotating speed of 200 r/min and reacted for 24 hours at the temperature of 25 ℃. After the reaction, 50 g of water was added while stirring, and after the stirring was stopped, diamond powder was precipitated to obtain a supernatant. Then 50 g of water is added into the diamond powder precipitate, the mixture is stirred and washed, and the supernatant is taken after the stirring is stopped. The washing process was repeated 4 times. The supernatants were combined, exchanged for 8 hours with 2.65 g of anion exchange resin and filtered, and then exchanged for 8 hours with 8.35 g of cation exchange resin and filtered. The filtrate was finally concentrated to 1.2%.
The aqueous polymer dispersion was left standing for 3 years without precipitation. The coating film does not crack and peel off, and the surface square resistance is 200 ohms under the condition of 70 percent of transparency.
As is clear from examples 1 to 5 and comparative example 1, the polymer particles without diamond powder were coarse, and precipitated a lot in water for 1 week, and the coating film was cracked and easily peeled off, and had low transparency. The electric conductivity is reduced by more than 10 times after the micro-jet homogenizer is crushed, and the requirement of industrial application cannot be met. The product added with the diamond powder for assisting polymerization has high conductivity and fine particles, can be stably dispersed in water for more than 3 years without precipitation, and does not need further crushing. The coating film does not crack or peel 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 easy to gel, and the method has the following beneficial effects:
1. in the polymerization process, the micro reaction tanks which are isolated from each other are formed by utilizing gaps among the micro powder, the gel is limited in a micro area, very fine polymer particles can be obtained, the polymer particles are stable and do not precipitate in water, and the conductivity of a polymerization product is not influenced;
2. the subsequent crushing step can be omitted by the aid of diamond powder polymerization, so that the production efficiency is improved;
3. the diamond powder can be recycled, so that economic loss is not increased, and pollutant discharge is not generated;
4. the artificial diamond powder is used as a common abrasive, is low in 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, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.
Claims (7)
1. A method for preparing a water-based polymer with the assistance of diamond micropowder is characterized by comprising the following steps: adding diamond micro powder in the process of preparing the water-based polymer, forming a micro-reaction tank by gaps among the diamond micro powder, and limiting gel in the micro-reaction tank to obtain the stable water-based polymer.
2. The method for preparing an aqueous polymer by the aid of diamond micropowder according to claim 1, wherein the diamond micropowder is added to the reaction vessel together with water and a reaction material, and a slurry is formed in the reaction vessel and reacted with stirring.
3. The method for preparing the water-based polymer by the aid of the diamond micropowder according to claim 1, wherein the water-based polymer and the diamond micropowder are separated by means of water-adding extraction after the water-based polymerization reaction is finished.
4. The method for preparing the water-based polymer by the aid of the diamond micropowder according to any one of claims 1 to 3, wherein the diamond micropowder has a particle size ranging from 0.1 to 20 μm.
5. The method for preparing the water-based polymer by the aid of the diamond micropowder according to any one of claims 1 to 3, wherein the impurity content of the diamond micropowder is less than one percent.
6. The method for preparing the water-based polymer by the aid of the diamond micropowder according to any one of claims 1 to 3, characterized in that 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 poly 4-vinyl benzene sulfonic acid, polyvinyl sulfonic acid, salt formed by the poly 4-vinyl benzene sulfonic acid and the polyvinyl sulfonic acid with alkali metal or alkaline earth metal, and copolymer thereof.
7. The method for preparing an aqueous polymer with the assistance of diamond micropowder according to any one of claims 1 to 3, characterized in that the solvent used in the process of preparing the aqueous polymer is water or a mixed solvent of water and an organic solvent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| US20060207946A1 (en) * | 2003-05-07 | 2006-09-21 | Ciba Specialty Chemicals Water Treatments 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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