CN115093407A - Method for preparing quinine iodosulfate nanorods in controllable manner under assistance of ball milling - Google Patents
Method for preparing quinine iodosulfate nanorods in controllable manner under assistance of ball milling Download PDFInfo
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- CN115093407A CN115093407A CN202210700560.2A CN202210700560A CN115093407A CN 115093407 A CN115093407 A CN 115093407A CN 202210700560 A CN202210700560 A CN 202210700560A CN 115093407 A CN115093407 A CN 115093407A
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- OCLTZILENWBWIY-HKPQTANOSA-N (r)-[(2s,4s,5r)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanol;molecular iodine;sulfuric acid;dihydroiodide Chemical compound I.I.II.II.OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 OCLTZILENWBWIY-HKPQTANOSA-N 0.000 title claims abstract description 61
- 238000000498 ball milling Methods 0.000 title claims abstract description 52
- 239000002073 nanorod Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 72
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims abstract description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 45
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims abstract description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000047 product Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000001258 Cinchona calisaya Nutrition 0.000 claims abstract description 36
- 229960000948 quinine Drugs 0.000 claims abstract description 36
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 21
- 239000011630 iodine Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000001576 FEMA 2977 Substances 0.000 claims description 11
- 229960003110 quinine sulfate Drugs 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 claims description 7
- KNAPFYNSANNXNM-UHFFFAOYSA-N [I].OS(O)(=O)=O Chemical compound [I].OS(O)(=O)=O KNAPFYNSANNXNM-UHFFFAOYSA-N 0.000 claims description 7
- -1 iodine metal compound Chemical class 0.000 claims description 4
- 239000001096 (4-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol hydrochloride Substances 0.000 claims description 2
- NNKXWRRDHYTHFP-HZQSTTLBSA-N (r)-[(2s,4s,5r)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanol;hydron;dichloride Chemical compound Cl.Cl.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 NNKXWRRDHYTHFP-HZQSTTLBSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960001811 quinine hydrochloride Drugs 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002245 particle Substances 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- PQLLEAYSRJFMFF-UHFFFAOYSA-N sulfuric acid;hydroiodide Chemical compound I.OS(O)(=O)=O PQLLEAYSRJFMFF-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000002070 nanowire Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000272814 Anser sp. Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000003410 quininyl group Chemical group 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D453/00—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids
- C07D453/02—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems
- C07D453/04—Heterocyclic compounds containing quinuclidine or iso-quinuclidine ring systems, e.g. quinine alkaloids containing not further condensed quinuclidine ring systems having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing quinine iodosulfate nanorods in a controllable manner by ball milling assistance, which comprises the following preparation steps: (1) mixing water, alcohol and acetic acid, adding sulfuric acid to adjust the pH value, then adding a quinine source, and uniformly mixing to obtain a solution A; (2) respectively dissolving an iodine simple substance and a metal compound of iodine in alcohol and water, and then mixing the two solutions to obtain a solution B; (3) mixing the solution A and the solution B, uniformly stirring for reaction, centrifuging after the reaction is finished, and collecting a reaction product; (4) dispersing the reaction product in a mixed solution of alcohol and water, and then heating and ultrasonically treating to obtain slurry C; (5) and mixing the slurry C with a grinding ball, carrying out ball milling treatment, and collecting a product after the ball milling is finished to obtain the quinine iodosulfate nanorod. The method prepares the quinine iodosulfate nanorod with proper size and good crystallinity and dispersibility by the aid of a coprecipitation technology and ball milling, and is suitable for being used as an SPD light valve material.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for preparing quinine iodosulfate nanorods in a controllable manner under the assistance of ball milling.
Background
A light valve is a device capable of adjusting luminous flux, and the research on the light valve has been half a century, and the light valve is generally classified into three types according to the principle of dimming: polymer Dispersed Liquid Crystals (PDLCs), electrochemical color changing devices (ECs) and Suspended Particle Devices (SPDs), wherein suspended particle devices are favored by more researchers due to their advantages of excellent weatherability, richer colors, high controllability of transparency, etc.
The electroactive component of the suspended particle device is a light modulating particle, and the light flux is modulated by the rearrangement of the suspended particles in the electric field. Quinine iodosulfate (Herapathite) nanorods have long been considered as the most suitable light modulating particles for suspended particle devices due to their very large dipole moment inside and their own blue, brown or wine-red appearance.
Reports on the preparation of quinine iodosulfate are commonly found in patents issued by the company of Research frontiers, and although these patents disclose basic preparation methods of the compounds, the industrialization process of SPD is slow, and the reasons for the slow progress are mainly that: (1) the length of the quinine iodine sulfate nanorods suitable for SPD is better below 1 μm, but the method provided by the prior patent has poor controllability, the dispersibility of the obtained product is poor, and the length is often more than micrometer and even dozens of micrometers, so that the requirement of the SPD light valve on the size of the dimming particles is difficult to meet; (2) the application scenario of the SPD device requires that the quinine iodosulfate particles have excellent weather resistance, and the quinine iodosulfate particles obtained by the conventional method are poor in crystallinity. Therefore, the preparation method of the quinine iodosulfate nanorod with good dispersibility, stable size and good crystallinity is very important.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing quinine iodide sulfate nanorods in a controllable manner by ball milling assistance, so that the quinine iodide sulfate nanorods with stable appearance and size and suitable for SPD devices are obtained.
A method for preparing iodine-sulfuric acid quinine nanorods in a controllable manner by ball milling assistance comprises the following preparation steps:
(1) mixing water, alcohol and acetic acid, adding sulfuric acid to adjust the pH value, then adding a quinine source, and uniformly mixing to obtain a solution A;
(2) respectively dissolving an iodine simple substance and a metal compound of iodine in alcohol and water, and then mixing the two solutions to obtain a solution B;
(3) mixing the solution A and the solution B, uniformly stirring for reaction, centrifuging after the reaction is finished, and collecting a reaction product;
(4) dispersing the reaction product in a mixed solution of alcohol and water, and then heating and ultrasonically treating to obtain slurry C;
(5) and mixing the slurry C with a grinding ball, carrying out ball milling treatment, and collecting a product after the ball milling is finished to obtain the iodine-sulfuric acid quinine nanorod.
In some embodiments, the mass ratio of water, alcohol and acetic acid in step (1) is 1: (0.5-1.2): (0.2-1.5), and preferably, the mass ratio of the water to the alcohol to the acetic acid is 1: (0.6-1.0): (0.5-1.0).
In some of these embodiments, the pH in step (1) ranges from 0.5 to 2, preferably the pH ranges from 1 to 1.5.
In some of these embodiments, the quinine source in step (1) is selected from at least one of quinine, quinine sulfate, quinine hydrochloride.
Further, the iodine metal compound in the step (2) is at least one selected from the group consisting of an alkali metal compound of iodine and an alkaline earth metal compound of iodine, preferably, the iodine metal compound is selected from the group consisting of NaI, KI, CaI 2 At least one of (1).
The iodine-quinine sulfate is a product formed by coordinating organic quinine molecules, sulfuric acid and inorganic iodine atoms/ions. Firstly, I is formed by the elementary iodine and the metal compound of iodine in the mixed solution of alcohol and water 3 - Ions then I 3 - Coordinating with quinine molecule adsorbed with hydrogen ion and sulfate radical to form amorphous product 4QH 2 2+ ·3SO 4 2- ·2I 3 - ·nH 2 O (Q represents a quinine molecule). The amorphous product has a linear shape I in the subsequent heating recrystallization process 3 - The ions are stacked gradually along the crystallographic b-axis to form a recrystallized framework, while quinine and sulfate fill the frameworkIn the middle, a crystalline nanowire product is formed.
In some embodiments, the mass ratio of alcohol to water in step (4) is 1: 5-20.
In some of the embodiments, the temperature of the heating in the step (4) is 50-90 ℃, and the time of the ultrasonic treatment is 20-120 min; preferably, the heating temperature is 60-80 ℃, and the ultrasonic treatment time is 25-50 min.
In some embodiments, the alcohol in step (1), step (2) and step (4) is at least one selected from monohydric alcohols and polyhydric alcohols such as methanol, ethanol, propanol and ethylene glycol.
In some of the embodiments, the size of the grinding balls in step (5) is 0.2-3mm, the time of the ball milling treatment is 0.5-12h, preferably, the size of the grinding balls is 0.5-2mm, and the time of the ball milling treatment is 3-5 h; in particular, zirconia balls can be selected as the grinding balls.
Ball milling is the process of crushing and mixing materials by the impact of falling milling bodies (balls, such as steel balls, goose hatching stones, etc.) and the milling action of the milling bodies and the inner wall of the ball mill, and is generally used for crushing large-sized objects visible to the naked eye. According to the method, zirconium balls with smaller diameters are used for ball milling of the product, and in the process, the zirconium balls and the product are directly collided, and the zirconium balls and the ball milling tank extrude the product, so that the length of the product is effectively shortened; it is worth mentioning that in the iodine-quinine sulfate product, the particles with larger length are more easily contacted with the zirconium balls, so that the particles with larger length are mainly subjected to size refinement in the ball milling process, and the nano rods with proper size are finally obtained. Because the substance is ground by mechanical stress in the ball milling process, the quinine iodosulfate belongs to organic-inorganic composite nanocrystals, the internal organic components cause the quinine iodosulfate to have weaker mechanical strength, and the direct ball milling treatment can cause the crystal structure to be dispersed, thereby causing the stability of the quinine iodosulfate nanomaterial to be reduced. According to the invention, the prepared quinine iodosulfate is subjected to ultrasonic treatment at a higher temperature before ball milling, so that the crystallinity of the quinine iodosulfate is improved, and the problem of insufficient mechanical strength caused by organic components in the quinine iodosulfate is solved.
In some of the embodiments, the quinine iodosulfate nanorods in step (5) have a diameter of less than 200nm and an aspect ratio of 2-10.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of obtaining a quinine iodosulfate nanowire product with stronger crystallinity and good dispersibility by heating and ultrasonic treatment through a coprecipitation technology, and then preparing the quinine iodosulfate nanorod with a proper size through ball milling assistance, wherein the prepared quinine iodosulfate nanorod has the average length of below 1 mu m, the diameter of below 200nm, the length-diameter ratio of less than 10, good durability and dispersibility, and is suitable for being used as a light-dimming particle of an SPD light valve.
(2) In the invention, quinine reacts with iodine simple substance and iodide ions in a sulfuric acid environment to obtain organic quinine, inorganic iodine and iodine-sulfuric acid coordinated quinine iodide precursor, then each component in the product is rearranged through heating recrystallization to form a nanowire with good crystallinity, and ultrasonic treatment is directly carried out at a higher temperature after heating, so that the recrystallized product has better dispersibility and more uniform size.
(3) The invention realizes the shaping and refining of the quinine iodosulfate nanocrystals with one-dimensional structures on the micro-nano size by utilizing ball milling treatment, and obtains the nanorods with the size suitable for SPD light valves. According to the invention, the iodine quinine sulfate is recrystallized and dispersed before ball milling, the mechanical property of the iodine quinine sulfate is enhanced, the internal microstructure of the iodine quinine sulfate is not damaged during ball milling treatment, and the crystal structure is not easy to collapse, so that the iodine quinine sulfate nanorod with more stable size can be obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of quinine iodosulfate nanorods prepared in example 1 of the present invention;
FIG. 2 is an SEM image of quinine iodosulfate nanorods prepared in example 1 of the present invention;
FIG. 3 is an SEM image of quinine iodosulfate nanorods prepared in example 2 of the present invention;
FIG. 4 is an SEM image of quinine iodosulfate nanorods prepared in example 3 of the present invention;
FIG. 5 is a comparative graph of XRD patterns of the quinine iodide sulfate precursor prepared in comparative example 1 and the quinine iodide sulfate nanorod obtained in example 1;
FIG. 6 is an SEM image of quinine iodosulfate precursor prepared in comparative example 1 of the present invention;
FIG. 7 is an SEM image of quinine iodosulfate product prepared in comparative example 2 of the present invention;
FIG. 8 is an SEM image of quinine iodosulfate product prepared in comparative example 3 of the present invention;
FIG. 9 is an SEM image of quinine iodosulfate product prepared in comparative example 4 of the present invention;
FIG. 10 is an SEM image of quinine iodosulfate product prepared in comparative example 5 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethanol and water according to the mass ratio of 2:8, heating the mixed solution to 80 ℃, transferring the heated mixed solution to an ultrasonic machine, and performing ultrasonic treatment for 30min to obtain dark brown slurry C;
(5) and mixing the slurry C with 20g of zirconia balls with the diameter of 1mm, placing the mixture in a ball milling tank for ball milling for 5 hours, and collecting a product after the ball milling is finished to obtain the quinine iodosulfate nanorod.
As shown in fig. 1, the XRD spectrum of the quinine iodosulfate nanorod prepared in example 1 is sharp, which indicates that the quinine iodosulfate nanorod prepared has high crystallinity and good stability; as shown in FIG. 2, which is the SEM image of the quinine iodide sulfate nanorods prepared in example 1, the quinine iodide sulfate nanorods can be seen to have an average length below 1 μm, a diameter below 200nm and an aspect ratio less than 5.
Example 2
(1) Stirring and mixing 100g of water, 60g of ethylene glycol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1.5, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g CaI 2 And 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of methanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethylene glycol and water according to the mass ratio of 1:9, heating the mixed solution to 60 ℃, transferring the heated mixed solution to an ultrasonic machine, and carrying out ultrasonic treatment for 30min to obtain dark brown slurry C;
(5) and mixing the slurry C with 20g of zirconia balls with the diameter of 1.5mm, placing the mixture in a ball milling tank for ball milling for 3 hours, and collecting a product after the ball milling is finished to obtain the quinine iodosulfate nanorod.
As shown in FIG. 3, which is the SEM image of the quinine iodosulfate nanorods prepared in example 2, it can be seen that the quinine iodosulfate nanorods have an average length below 1 μm, a diameter below 200nm, and an aspect ratio less than 5.
Example 3
(1) Stirring and mixing 100g of water, 60g of ethylene glycol and 100g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 6g of quinine sulfate into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g CaI 2 And 2g I 2 Dissolving the two solutions in 50g of water and 5g of methanol respectively, and mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethylene glycol and water according to the mass ratio of 1:9, heating the mixed solution to 90 ℃, transferring the heated mixed solution to an ultrasonic machine, and carrying out ultrasonic treatment for 30min to obtain dark brown slurry C;
(5) and mixing the slurry C with 20g of zirconia balls with the diameter of 2mm, placing the mixture into a ball milling tank for ball milling for 3 hours, and collecting a product after the ball milling is finished to obtain the iodine-sulfuric acid quinine nanorods.
As shown in FIG. 4, which is the SEM image of the quinine iodide sulfate nanorods prepared in example 3, it can be seen that the quinine iodide sulfate nanorods have an average length below 2 μm, a diameter below 200nm, and an aspect ratio less than 10.
Comparative example 1
This comparative example includes most of the operating steps of example 1, except that no heating, sonication, and ball milling treatments were performed. The preparation method comprises the following steps:
(1) stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) and pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product to obtain an iodine-sulfuric acid quinine precursor.
FIG. 5 is a comparison graph of XRD spectra of the quinine iodosulfate precursor prepared in the comparative example 1 and the quinine iodosulfate nanorod prepared in the example 1, and it can be seen that the intensity of the characteristic peak of the quinine iodosulfate precursor is very low, which indicates that the quinine iodosulfate prepared in the comparative example 1 has poor crystallinity; fig. 6 shows an SEM image of the quinine iodosulfate precursor prepared in comparative example 1, and it can be seen that the product is an amorphous agglomerate.
Comparative example 2
This comparative example includes most of the operating steps of example 1, except that the heating is not followed by sonication and ball milling. The preparation method comprises the following steps:
(1) stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I2, respectively dissolving the KI and 2g I2 in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethanol and water according to the mass ratio of 2:8, heating the mixed solution to 80 ℃, cooling, and collecting the product to obtain the quinine iodosulfate.
FIG. 7 is an SEM image of the quinine iodosulfate product prepared in comparative example 2, and it can be seen that the length of the quinine iodosulfate nanowire prepared is more than 10 μm, the aspect ratio is very high, and the dispersibility is poor.
Comparative example 3
This comparative example includes most of the operating steps of example 1 except that no sonication was performed prior to the ball milling process. The preparation method comprises the following steps:
(1) stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethanol and water according to the mass ratio of 2:8, and then heating the mixed solution to 80 ℃ to obtain dark brown slurry C;
(5) and mixing the slurry C with 20g of zirconia balls with the diameter of 1mm, placing the mixture into a ball milling tank for ball milling for 5 hours, and collecting a product after the ball milling is finished to obtain the iodine-sulfuric acid quinine.
As shown in fig. 8, which is an SEM image of the quinine iodosulfate product prepared in comparative example 3, it can be seen that the prepared quinine iodosulfate nanowires are not ball-milled into short rods, but rather, the agglomeration is increasingly serious.
Comparative example 4
This comparative example includes most of the operating steps of example 1, except that no ball milling treatment was performed after sonication. The preparation method comprises the following steps:
(1) stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethanol and water according to the mass ratio of 2:8, heating the mixed solution to 80 ℃, transferring the heated mixed solution to an ultrasonic machine, carrying out ultrasonic treatment for 30min, and collecting the product to obtain the quinine iodosulfate.
FIG. 9 is an SEM image of the quinine iodosulfate product prepared in comparative example 4, and it can be seen that the quinine iodosulfate particles prepared have an average length of more than 10 μm, a diameter of less than 200nm, an aspect ratio of more than 50, and are nano-linear particles.
Comparative example 5
This comparative example includes most of the operating steps of example 1, except that the heating and cooling are followed by ultrasonic and ball milling treatments. The preparation method comprises the following steps:
(1) stirring and mixing 100g of water, 100g of ethanol and 50g of acetic acid uniformly, adding concentrated sulfuric acid to adjust the pH value to 1, then adding 5g of quinine into the obtained solution, and mixing uniformly to obtain a light yellow solution A;
(2) weighing 1.2g of KI and 2g I 2 Respectively dissolving the two solutions in 50g of water and 10g of ethanol, and then mixing the two solutions to obtain a dark purple solution B;
(3) pouring the solution B into the solution A, uniformly stirring, reacting for 1h, and then centrifuging and collecting a reaction product;
(4) weighing 2g of reaction product, dispersing the reaction product in 40g of mixed solution prepared from ethanol and water according to the mass ratio of 2:8, heating the mixed solution to 80 ℃, cooling and crystallizing, transferring the cooled mixed solution to an ultrasonic machine, and carrying out ultrasonic treatment for 30min to obtain dark brown slurry C;
(5) and mixing the slurry C with 20g of zirconia balls with the diameter of 1mm, placing the mixture in a ball milling tank for ball milling for 5 hours, and collecting a product after the ball milling is finished to obtain the quinine iodosulfate.
As shown in FIG. 10, which is an SEM image of the quinine iodosulfate product prepared in comparative example 5, it can be seen that the prepared quinine iodosulfate nanorods are seriously agglomerated and have non-uniform size distribution.
Examples 1-3 are quinine iodosulfate nanorods prepared by the present invention, with average length below 2 μm, diameter below 200nm, aspect ratio less than 10, and good crystallinity and dispersibility, suitable for use as a light modulating particle for SPD light valves. Comparative examples 1-4 do not contain complete heating, ultrasonic and ball milling operations, the prepared quinine iodosulfate is an amorphous aggregate, or has the problems of overlarge size and poor dispersibility/crystallinity, and comparative example 5 is subjected to ultrasonic and ball milling treatment after recrystallization is completed, so that the size distribution is uneven, and clustering phenomenon is easy to occur.
In conclusion, the invention obtains the iodine-quinine sulfate product with stronger crystallinity by heating and ultrasonic processing through a coprecipitation technology, and then obtains the iodine-quinine sulfate nanorod with proper size through ball milling assistance. The method not only solves the defects of poor dispersibility and low crystallinity of the quinine iodosulfate product in the prior patent, but also improves the current situation of overlarge size of the quinine iodosulfate product in the prior patent, and an ideal product can be obtained by proper ball milling. In addition, the invention improves the dispersibility of the quinine iodosulfate particles by means of ultrasound, and is beneficial to improving the applicability of the product in dimming products. The smooth implementation of the scheme provided by the invention is expected to break the blockade of European and American countries on SPD technology and promote the commercialization process of SPD.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (10)
1. The method for preparing the quinine iodosulfate nanorods in a controllable manner under the assistance of ball milling is characterized by comprising the following preparation steps:
(1) mixing water, alcohol and acetic acid, adding sulfuric acid to adjust the pH value, then adding a quinine source, and uniformly mixing to obtain a solution A;
(2) respectively dissolving elementary iodine and a metal compound of iodine in alcohol and water, and then mixing the two solutions to obtain a solution B;
(3) mixing the solution A and the solution B, uniformly stirring for reaction, centrifuging after the reaction is finished, and collecting a reaction product;
(4) dispersing the reaction product in a mixed solution of alcohol and water, and then heating and ultrasonically treating to obtain slurry C;
(5) and mixing the slurry C with a grinding ball, carrying out ball milling treatment, and collecting a product after the ball milling is finished to obtain the iodine-sulfuric acid quinine nanorod.
2. The method according to claim 1, wherein the mass ratio of the water, the alcohol and the acetic acid in the step (1) is 1: (0.5-1.2): (0.2-1.5).
3. The method according to claim 1, wherein the pH in step (1) is in the range of 0.5 to 2.
4. The process of claim 1, wherein the quinine source in step (1) is selected from at least one of quinine, quinine sulfate, quinine hydrochloride.
5. The method according to claim 1, wherein the iodine metal compound in the step (2) is at least one selected from the group consisting of an alkali metal compound of iodine and an alkaline earth metal compound of iodine.
6. The method according to claim 1, wherein the mass ratio of the alcohol to the water in the step (4) is 1: 5-20.
7. The method according to claim 1, wherein the temperature of the heating in the step (4) is 50-90 ℃ and the time of the ultrasonic treatment is 20-120 min.
8. The method according to claim 1, wherein the alcohol in step (1), step (2) and step (4) is at least one selected from monohydric alcohols and polyhydric alcohols such as methanol, ethanol, propanol and ethylene glycol.
9. The method as claimed in claim 1, wherein the size of the grinding balls in the step (5) is 0.2 to 3mm, and the time of the ball milling treatment is 0.5 to 12 hours.
10. The method of claim 1, wherein the diameter of the quinine iodosulfate nanorods in step (5) is less than 200nm, and the aspect ratio is 2-10.
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| CN202210700560.2A CN115093407B (en) | 2022-06-20 | Method for controllably preparing quinine iodized sulfate nanorods with assistance of ball milling |
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| CN202210700560.2A CN115093407B (en) | 2022-06-20 | Method for controllably preparing quinine iodized sulfate nanorods with assistance of ball milling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB429925A (en) * | 1932-12-03 | 1935-06-04 | Edwin Herbert Land | New and improved colloidal suspensions and the process of making same |
| GB525956A (en) * | 1937-12-04 | 1940-09-09 | Polaroid Corp | Improvements relating to processes for the manufacture of polarizing materials |
| US2289712A (en) * | 1937-12-04 | 1942-07-14 | Polaroid Corp | Process for the manufacture of polarizing materials |
| JPS4820560B1 (en) * | 1969-06-26 | 1973-06-21 | ||
| US4877313A (en) * | 1986-09-30 | 1989-10-31 | Research Frontiers Incorporated | Light-polarizing materials and suspensions thereof |
| JPH09105966A (en) * | 1995-10-12 | 1997-04-22 | Toyota Central Res & Dev Lab Inc | Nonlinear optical material and method for utilizing the same |
| CN1308716A (en) * | 1998-07-09 | 2001-08-15 | 尖端研究公司 | Light-polarizing particles of improved particle size distribution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB429925A (en) * | 1932-12-03 | 1935-06-04 | Edwin Herbert Land | New and improved colloidal suspensions and the process of making same |
| GB525956A (en) * | 1937-12-04 | 1940-09-09 | Polaroid Corp | Improvements relating to processes for the manufacture of polarizing materials |
| US2289712A (en) * | 1937-12-04 | 1942-07-14 | Polaroid Corp | Process for the manufacture of polarizing materials |
| JPS4820560B1 (en) * | 1969-06-26 | 1973-06-21 | ||
| US4877313A (en) * | 1986-09-30 | 1989-10-31 | Research Frontiers Incorporated | Light-polarizing materials and suspensions thereof |
| JPH09105966A (en) * | 1995-10-12 | 1997-04-22 | Toyota Central Res & Dev Lab Inc | Nonlinear optical material and method for utilizing the same |
| CN1308716A (en) * | 1998-07-09 | 2001-08-15 | 尖端研究公司 | Light-polarizing particles of improved particle size distribution |
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