CN116515343A - Retinoic acid/water magnesite composite powder and preparation method and application thereof - Google Patents
Retinoic acid/water magnesite composite powder and preparation method and application thereof Download PDFInfo
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- CN116515343A CN116515343A CN202310594588.7A CN202310594588A CN116515343A CN 116515343 A CN116515343 A CN 116515343A CN 202310594588 A CN202310594588 A CN 202310594588A CN 116515343 A CN116515343 A CN 116515343A
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- retinoic acid
- water
- composite powder
- magnesite
- water magnesite
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- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 title claims abstract description 173
- 229930002330 retinoic acid Natural products 0.000 title claims abstract description 173
- 229960001727 tretinoin Drugs 0.000 title claims abstract description 173
- 239000000843 powder Substances 0.000 title claims abstract description 163
- 239000001095 magnesium carbonate Substances 0.000 title claims abstract description 161
- 229910000021 magnesium carbonate Inorganic materials 0.000 title claims abstract description 161
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 155
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 149
- 235000014380 magnesium carbonate Nutrition 0.000 title claims abstract description 145
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002989 correction material Substances 0.000 claims abstract description 58
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000006482 condensation reaction Methods 0.000 claims abstract description 20
- 230000018044 dehydration Effects 0.000 claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- 238000000967 suction filtration Methods 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 238000004108 freeze drying Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003063 flame retardant Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 58
- 239000007787 solid Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 229930014626 natural product Natural products 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 229910052599 brucite Inorganic materials 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000008239 natural water Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005518 chemical engineering design Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960003471 retinol Drugs 0.000 description 1
- 235000020944 retinol Nutrition 0.000 description 1
- 239000011607 retinol Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D10/00—Correcting fluids, e.g. fluid media for correction of typographical errors by coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides retinoic acid/water magnesite composite powder, a preparation method and application thereof, wherein the retinoic acid/water magnesite composite powder consists of retinoic acid and water magnesite, wherein retinoic acid is an outer shell of the composite powder, water magnesite is an inner core of the composite powder, and the molar ratio of retinoic acid to water magnesite is 1-50:1. The retinoic acid/water magnesite composite powder is prepared by sequentially mixing a water magnesite solution and a dehydrating agent dispersion liquid with a retinoic acid solution, and then carrying out dehydration condensation reaction. The retinoic acid/water magnesite composite powder has a retinoic acid layer on the surface, has a flexible conjugated structure, can release weak light signals in low-viscosity correction fluid and release strong light signals in high-viscosity correction fluid, and is beneficial to the formula design of the correction fluid. And the conjugated structure of retinoic acid can lead the retinoic acid to be very easy to form carbon in the combustion process, and has better synergistic flame retardant effect with the internal water magnesite.
Description
Technical Field
The invention relates to the technical field of photochemical detection, in particular to retinoic acid/water magnesite composite powder, and a preparation method and application thereof.
Background
The correction fluid is a white opaque pigment which is used for covering wrongly written characters and can be repeatedly written, and is widely applied to various stationery paper operations, and the correction effect of the correction fluid is deep. The inside of the liquid is mainly provided with a plurality of components such as trichloroethane, methylcyclohexane, cyclohexane and the like, and also comprises inorganic powder such as calcium carbonate and the like which provide covering power, and the liquid is usually required to be used in a period of time in daily use, because the liquid can be layered with the filler due to long-term storage, and the solvent is relatively volatile, so that correction fluid is very easy to be sticky. Furthermore, as an emulsion, the amount of solvent added during the preparation process can also profoundly affect the correction effect of the correction fluid. All the components are related to the viscosity, the viscosity is too low, the fluidity is improved, but the fluidity is easy to cause too thin coating, and the covering power is reduced; in contrast, the viscosity is too high, the fluidity is reduced and the coating is too thick, the hiding power is improved to a certain extent, but the solid content is relatively high at this time, and the cost is increased. Therefore, a functional material for detecting the viscosity of the correction fluid, which is quick, convenient and visual, even has a certain covering property, can sense the viscosity change by the intensity of the release of the optical signal, and has important practical significance for the efficient development and application of the correction fluid.
In general, in addition to the addition of inorganic powders to meet the most basic hiding power, the correction fluid needs to be added with a portion of flame retardant to avoid accidental burning of the correction fluid during storage and use due to uncontrollable factors. From another aspect, the correction fluid has higher requirements on the viscosity of the micro-region in the preparation process, most of the existing analysis and detection means are strongly dependent on equipment, and the existing analysis and detection means are usually used for measuring macroscopic viscosity, so that visual imaging is difficult to perform on a molecular level, and compared with the photochemical analysis technology of fusing natural product functional organic molecules, the photochemical analysis technology has remarkable advantages in functions such as detection sensitivity, imaging timeliness and operation convenience, and particularly has relatively sensitive response to viscosity change of the micro-region. The loading of various kinds of sensors with photochemical functions on inorganic powder further makes the development of powder platforms with various capabilities have been developed as one of the core means for solving the problems in recent years. Therefore, development of multifunctional composite powder capable of simultaneously meeting requirements of better covering power, flame retardant effect and micro-area viscosity measurement is needed, and the strategy has become a trend in improving the high-value application of the traditional inorganic powder.
Disclosure of Invention
The invention aims to provide retinoic acid/water magnesite composite powder as well as a preparation method and application thereof, and aims to solve the technical problems that correction fluid has poor covering power and flame retardant effect and micro-area viscosity detection cannot be visualized in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides retinoic acid/water magnesite composite powder, which consists of retinoic acid and water magnesite, wherein retinoic acid is an outer shell of the composite powder, and water magnesite is an inner core of the composite powder; the mol ratio of the retinoic acid to the water magnesite is 1-50:1.
Preferably, the retinoic acid/water magnesite composite powder D 50 0.9-3.0 μm, wherein D of the core 50 0.8-2.8 mu m.
The invention provides a preparation method of retinoic acid/water magnesite composite powder, which comprises the following steps: sequentially mixing the water magnesite solution and the dehydrating agent dispersion liquid with the retinoic acid solution, and then carrying out dehydration condensation reaction to obtain retinoic acid/water magnesite composite powder.
Preferably, the retinoic acid solution is formed by mixing retinoic acid and a solvent; the water magnesite solution is formed by mixing water magnesite and a solvent; the dehydrating agent dispersion liquid is formed by mixing a dehydrating agent and a solvent; the solvent independently comprises one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, water and ethyl acetate.
Preferably, the concentration of the retinoic acid solution is 1-500 mol/L; the concentration of the water magnesite solution is 1-4 mol/L; the content of the dehydrating agent in the dehydrating agent dispersion liquid is 1-1000 mol/L.
Preferably, the dehydrating agent comprises K 2 CO 3 、Cs 2 CO 3 、CaCO 3 、Na 2 CO 3 、NaHCO 3 And Ca (OH) 2 One of the following;
the molar ratio of the dehydrating agent to the water magnesite is 1-1000: 1.
preferably, the dehydration condensation reaction is carried out at a temperature of 45 to 100 ℃ for a time of 1 to 60 hours.
Preferably, the product of the dehydration condensation reaction is sequentially subjected to suction filtration precipitation, centrifugal washing and freeze drying; the freeze drying temperature is-70 to-5 ℃, and the freeze drying time is 1 to 96 hours.
The invention provides an application of retinoic acid/water magnesite composite powder in correction fluid, which is prepared by mixing retinoic acid/water magnesite composite powder with correction fluid.
Preferably, the mixing concentration of the retinoic acid/water magnesite composite powder is 0.1-20 mu mol/L.
The retinoic acid/water magnesite composite powder provided by the invention is prepared by combining natural retinoic acid and natural magnesium salt together through chemical bonds (shown in figure 1). The functional composite powder is added into correction fluid with different viscosities, retinoic acid on the surface of the functional composite powder is provided with a plurality of freely rotatable flexible conjugate structures, the retinoic acid can freely rotate in a low-viscosity solution environment, the excited energy can be consumed in a mechanical dissipation mode, a non-radiation transition mode is shown, so that a released optical signal is weaker or even disappears, in a high-viscosity correction fluid environment, the free rotation of the retinoic acid is limited, a channel which returns to a ground state originally through the non-radiation transition is closed, and the retinoic acid returns to the ground state through the radiation transition mode, so that a strong fluorescent signal is released, the phenomenon is closely related to the physical viscosity of the correction fluid, the consistency of the correction fluid formula design can be judged in an auxiliary mode through the strength of the released optical signal, and the design can realize visual tracking of the formulas of different correction fluids (a specific detection mechanism is shown in a figure 3); moreover, the water magnesite has higher whiteness, is basic magnesium carbonate, and is a compound of magnesium carbonate and magnesium hydroxide, and has natural advantages in flame retardance and smoke suppression.
The invention has the beneficial effects that:
(1) The invention adopts the brucite powder widely existing in nature as the main body of the functional material, has higher whiteness, has better flame retardance and smoke suppression characteristics, can meet the covering power and flame retardance requirements of the correction fluid inorganic powder, and is most critical that the brucite powder is derived from nature and can obtain ultrafine powder through physical grinding and classified winnowing;
(2) The retinoic acid/water magnesite composite powder provided by the invention has a layer of retinoic acid on the surface, is one of retinol substances commonly existing in nature, has a flexible conjugated structure, can release weak light signals in low-viscosity correction fluid, and release strong light signals in high-viscosity correction fluid, thereby being beneficial to the formulation design of the correction fluid and greatly expanding the application scene of natural products in various environments;
(3) The retinoic acid/water magnesite composite powder provided by the invention has a plurality of conjugated structures, so that the retinoic acid is very easy to char in the combustion process, is a typical natural char forming agent, and has good synergistic flame retardant effect with internal water magnesite for improving the flame retardant property of the composite powder and providing a physical shielding layer in a condensed phase to inhibit the impact of airflow, mass flow and heat flow;
(4) The retinoic acid/water magnesite composite powder provided by the invention is prepared by adopting a one-step method, the preparation process is simple, the main raw materials used are all from the nature, and belong to typical natural products, the retinoic acid/water magnesite composite powder is very friendly to the environment, can be easily subjected to chemical engineering design, can realize mass production, is suitable for large-scale industrial application, does not have a complex post-treatment process, and is relatively low in price and low in comprehensive application cost.
Drawings
FIG. 1 is a schematic structural diagram of retinoic acid/water magnesite composite powder prepared in examples 1-3;
FIG. 2 is an SEM image of retinoic acid/water-magnesite composite powder prepared in example 1;
FIG. 3 is a schematic diagram showing the induction mechanism of retinoic acid/water magnesite composite powder prepared in examples 1-3 to low viscosity and high viscosity correction fluid;
FIG. 4 is a spectrum of retinoic acid/water magnesite composite powder prepared in example 1 in solutions with different viscosities;
FIG. 5 is a plot of the logarithmic function linear fit of fluorescence intensity and solution viscosity for retinoic acid/water magnesite composite powder prepared in example 1;
FIG. 6 is a graph showing the absorption spectra of retinoic acid/water magnesite composite powder prepared in example 1 in solutions of different polarities;
FIG. 7 is a photo-stability test chart of retinoic acid/water magnesite composite powder prepared in example 1;
FIG. 8 is a graph showing the release of optical signals from retinoic acid/water-magnesite composite powder prepared in example 1 in correction slurries of different viscosities.
Detailed Description
The brucite powder used in the invention is prepared by a physical grinding method, and the brucite powder with proper grain size is generally selected by ball milling for multiple times and air classification.
The invention provides retinoic acid/water magnesite composite powder, which consists of retinoic acid and water magnesite, wherein retinoic acid is an outer shell of the composite powder, and water magnesite is an inner core of the composite powder; the mol ratio of the retinoic acid to the water magnesite is 1-50:1.
In the invention, retinoic acid is a naturally occurring organic small molecule, the specific chemical structural formula is shown as formula I, and the retinoic acid is fully called 3, 7-dimethyl-9- (2, 6-trimethylcyclohex-1-en-1-yl) non-2, 4,6,8-Tetraenoic acid, DTCT for short, with molecular formula of C 20 H 28 O 2 The relative molecular mass was 300.20.
In the present invention, the molar ratio of retinoic acid to hydromagnesite is preferably 2 to 45:1, and more preferably 4 to 40:1.
In the invention, when the molar ratio of retinoic acid to water magnesite is lower than 1:1, the content of surface retinoic acid is relatively low, the composite effect on water magnesite is limited, the induction measurement of viscosity and the flame retardant effect are possibly low, and the comprehensive performance is reduced; on the other hand, when the molar ratio of retinoic acid to water-magnesite is greater than 50:1, the concentration of surface retinoic acid may be too high, and too much retinoic acid may encapsulate a plurality of water-magnesite particles together, which may result in larger water-magnesite particles, and have a greater influence on the final hiding power, flame-retarding effect, and viscosity response during the preparation process.
In the invention, the retinoic acid/water magnesite composite powder D 50 0.9 to 3.0. Mu.m, preferably 1.0 to 2.8. Mu.m, more preferably 1.2 to 2.6. Mu.m; wherein D of the kernel 50 The particle size is 0.8 to 2.8. Mu.m, preferably 1.2 to 2.6. Mu.m, more preferably 1.4 to 2.4. Mu.m.
The invention provides a preparation method of retinoic acid/water magnesite composite powder, which comprises the following steps: sequentially mixing the water magnesite solution and the dehydrating agent dispersion liquid with the retinoic acid solution, and then carrying out dehydration condensation reaction to obtain retinoic acid/water magnesite composite powder.
In the present invention, the process of the dehydration condensation reaction is as follows:
in the invention, the retinoic acid solution is formed by mixing retinoic acid and a solvent; the water magnesite solution is formed by mixing water magnesite and a solvent; the dehydrating agent dispersion liquid is formed by mixing a dehydrating agent and a solvent; the solvent independently comprises one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, water and ethyl acetate, preferably one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide, and more preferably one or more of ethanol, tetrahydrofuran and N, N-dimethylformamide.
In the present invention, the retinoic acid solution is formulated, preferably under stirring conditions, wherein the stirring speed is 100 to 900rpm, preferably 200 to 800rpm, further preferably 300 to 700rpm; the stirring temperature is 20-45 ℃, preferably 25-40 ℃, and more preferably 30-35 ℃; the stirring time is 10 to 150 minutes, preferably 30 to 130 minutes, and more preferably 50 to 100 minutes.
In the present invention, the aqueous magnesite solution is preferably stirred at a stirring speed of 100 to 1300rpm, preferably 200 to 1200rpm, and more preferably 400 to 1000rpm; the stirring temperature is 20-50 ℃, preferably 25-45 ℃, and more preferably 30-40 ℃; the stirring time is 10 to 300 minutes, preferably 40 to 270 minutes, and more preferably 60 to 240 minutes.
In the present invention, the aqueous magnesite solution and the retinoic acid solution are preferably mixed by dropwise addition, wherein the dropwise addition rate is 1 drop/s to 1 drop/10 s, preferably 1 drop/2 s to 1 drop/8 s, and more preferably 1 drop/3 s to 1 drop/5 s.
In the present invention, the concentration of the retinoic acid solution is 1 to 500mol/L, preferably 2 to 400mol/L, and more preferably 5 to 350mol/L; the concentration of the water magnesite solution is 1-4 mol/L, preferably 1.5-3.5 mol/L, and more preferably 2-3 mol/L; the content of the dehydrating agent in the dehydrating agent dispersion is 1 to 1000mol/L, preferably 10 to 900mol/L, and more preferably 20 to 800mol/L.
In the present invention, the dehydrating agent comprises K 2 CO 3 、Cs 2 CO 3 、CaCO 3 、Na 2 CO 3 、NaHCO 3 And Ca (OH) 2 One of them, preferably K 2 CO 3 、Cs 2 CO 3 、Na 2 CO 3 And NaHCO 3 One or more of them, more preferably K 2 CO 3 、Cs 2 CO 3 And Na (Na) 2 CO 3 One or more of them.
In the invention, the mole ratio of the dehydrating agent to the water magnesite is 1-1000: 1, preferably 2 to 900:1, and more preferably 4 to 800:1.
In the present invention, the temperature of the dehydration condensation reaction is 45 to 100 ℃, preferably 50 to 90 ℃, and more preferably 60 to 80 ℃; the dehydration condensation reaction time is 1 to 60 hours, preferably 5 to 55 hours, more preferably 10 to 50 hours.
In the present invention, the dehydration condensation reaction is carried out under stirring conditions, wherein the stirring speed is 100 to 1500rpm, preferably 200 to 1300rpm, and more preferably 300 to 1100rpm.
In the present invention, the product of the dehydration condensation reaction is sequentially subjected to suction filtration precipitation, centrifugal washing and freeze drying.
In the invention, the suction filtration precipitation is carried out in two steps, the first step is suction filtration, the second step is precipitation, the suction filtration is carried out on liquid after the dehydration condensation reaction is finished, wherein quick or medium-speed filter paper is adopted in the suction filtration process, the vacuum degree is controlled to be-0.098 to-0.07 MPa, preferably-0.09 to-0.075 MPa, further preferably-0.085 to-0.08 MPa, and the suction filtration process is repeatedly carried out by using a solvent for flushing the suction filtration, wherein the solvent is one or a mixture of methanol, ethanol and deionized water, preferably methanol and/or ethanol, further preferably ethanol; the precipitation is to re-disperse the solid powder after suction filtration in ethanol, then to perform standing precipitation, and remove supernatant, wherein the time of standing precipitation is 1-48 hours, preferably 5-40 hours, and more preferably 10-35 hours.
In the invention, the centrifugal washing is to add the solid product precipitated by suction filtration into deionized water for a plurality of times, and the solid content of the solid product in the deionized water is controlled to be 1-20 g/mL, preferably 3-18 g/mL, and more preferably 5-15 g/mL; the centrifugation speed is 1000 to 10000rpm, preferably 1500 to 9000rpm, and more preferably 2000 to 7000rpm; the centrifugation time is 3 to 60 minutes, preferably 10 to 50 minutes, and more preferably 20 to 40 minutes.
In the invention, the temperature of freeze drying is-70 to-5 ℃, preferably-65 to-10 ℃, and further preferably-55 to-15 ℃; the time for freeze-drying is 1 to 96 hours, preferably 5 to 90 hours, and more preferably 10 to 80 hours.
The invention provides an application of retinoic acid/water magnesite composite powder in correction fluid, which is prepared by mixing retinoic acid/water magnesite composite powder with correction fluid.
In the present invention, the mixing concentration of the retinoic acid/water-magnesite composite powder is 0.1 to 20. Mu. Mol/L, preferably 1 to 18. Mu. Mol/L, and more preferably 5 to 15. Mu. Mol/L.
In the present invention, when the retinoic acid/water-magnesite composite powder and the correction fluid are mixed, it is preferable to perform the mixing under stirring conditions, wherein the stirring speed is 50 to 500rpm, preferably 100 to 400rpm, and more preferably 150 to 350rpm; the stirring temperature is 20-45 ℃, preferably 25-40 ℃, and more preferably 30-35 ℃; the stirring time is 1 to 12 hours, preferably 2 to 10 hours, more preferably 4 to 8 hours.
The retinoic acid/water magnesite composite powder provided by the invention is applied to correction fluid, not only can provide better covering power, but also has better flame retardant property, can effectively improve the combustion inhibition property of the correction fluid, not only can realize detection and imaging of a physical key index of micro-area viscosity in the preparation process, and provides a beneficial reference for the formula design of the correction fluid, and based on the retinoic acid/water magnesite composite powder, the retinoic acid/water magnesite composite powder is a functional powder which further realizes multiple purposes on the basis of the traditional water magnesite powder.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
In the present invention, D of the hydromagnesite powder used in examples 1 to 3 and comparative examples 1 to 2 50 Is 2.8 μm.
Example 1
Dissolving 100mol of retinoic acid in N, N dimethylformamide, and stirring at a speed of 400rpm at 25 ℃ for 80min to obtain a retinoic acid solution with a concentration of 100 mol/L; 4mol of the water magnesite powder is dispersed in N, N dimethylformamide, and stirred at the speed of 800rpm for 120min at the temperature of 30 ℃ to obtain the water magnesite solution with the concentration of 4 mol/L. Then dripping the water magnesite solution into the retinoic acid solution, wherein the dripping speed is 1 drop/5 s, and 1L of K is added after the dripping is finished 2 CO 3 Adding the dispersion into the mixed solution, wherein K 2 CO 3 The dispersion liquid is composed of K 2 CO 3 And N, N dimethylformamide, K 2 CO 3 The content of (2) is 100mol/L, dehydration condensation reaction is carried out at 60 ℃, the stirring speed is 1000rpm during the reaction, and the reaction time is controlled to be 24 hours; after the reaction is finished, sequentially carrying out suction filtration and precipitation, centrifugal washing and freeze drying on the reaction product, wherein the specific steps are as follows: the rapid filter paper is adopted in the suction filtration process, the vacuum degree is controlled to be-0.098 MPa, and ethanol is repeatedly used for flushing and suction filtration in the suction filtration process; the solid powder after suction filtration is redispersed in ethanol, and is settled for 12 hours, and the supernatant is removed; dispersing the solid powder after suction filtration and precipitation in deionized water, wherein the solid content of the solid powder in the deionized water is 10g/mL, and then placing the solid powder in a centrifugal machine for centrifugal washing, wherein the adopted centrifugal speed is 6000rpm, and the centrifugal time is 30min; and (3) after centrifugal washing for three times, placing the solid powder into a low-temperature dryer for freeze drying, wherein the freeze drying temperature is-45 ℃, and the freeze drying time is 32 hours, so as to obtain the retinoic acid/water magnesite composite powder.
Fig. 2 is an SEM image of the retinoic acid/water magnesite composite powder prepared in example 1, and as can be seen from fig. 2, various granular materials are attached to the surface of the water magnesite powder, the surface is rough but continuous and compact, the edges of the respective particles are clear and relatively independent, and the composite powder has a good coating effect (as shown in a circle in the figure).
Example 2
1mol of retinoic acid is dissolved in ethanol and stirred at a rate of 100rpm for 150min at 20 ℃,obtaining retinoic acid solution with the concentration of 1 mol/L; 1mol of the brucite powder is dispersed in ethanol and stirred at the speed of 100rpm for 30min at the temperature of 20 ℃ to obtain a brucite solution with the concentration of 1 mol/L. Then dripping the water magnesite solution into the retinoic acid solution, wherein the dripping speed is 1 drop/10 s, and then dripping 1L of Cs 2 CO 3 Adding the dispersion into the mixed solution, wherein Cs 2 CO 3 The dispersion liquid is composed of Cs 2 CO 3 Is prepared with ethanol and Cs 2 CO 3 The content of (2) is 100mol/L, the dehydration condensation reaction is carried out at 45 ℃, the stirring speed is 1500rpm during the reaction, and the reaction time is controlled to be 60 hours; after the reaction is finished, sequentially carrying out suction filtration and precipitation, centrifugal washing and freeze drying on the reaction product, wherein the specific steps are as follows: the rapid filter paper is adopted in the suction filtration process, the vacuum degree is controlled to be-0.07 MPa, and ethanol is repeatedly used for washing and suction filtration in the suction filtration process; the solid powder after suction filtration is redispersed in ethanol, and is settled for 48 hours, and the supernatant is removed; dispersing the solid powder after suction filtration and precipitation in deionized water, wherein the solid content of the solid powder in the deionized water is 1g/mL, and then placing the solid powder in a centrifugal machine for centrifugal washing, wherein the adopted centrifugal speed is 1000rpm, and the centrifugal time is 60min; and (3) after centrifugal washing for three times, placing the solid powder into a low-temperature dryer for freeze drying, wherein the freeze drying temperature is-70 ℃, and the freeze drying time is 1h, so as to obtain the retinoic acid/water magnesite composite powder.
Example 3
Dissolving 100mol of retinoic acid in dimethyl sulfoxide, and stirring at a speed of 900rpm at 45 ℃ for 10min to obtain a retinoic acid solution with a concentration of 400 mol/L; 2mol of the water magnesite powder is dispersed in dimethyl sulfoxide, and stirred at a speed of 1300rpm for 10min at 50 ℃ to obtain a water magnesite solution with a concentration of 2 mol/L. Then dripping the water magnesite solution into the retinoic acid solution, wherein the dripping speed is 1 drop/s, and 1L of Na is added after the dripping is finished 2 CO 3 Adding the dispersion into the mixed solution, wherein Na 2 CO 3 The dispersion liquid is prepared from Na 2 CO 3 Is prepared with ethanol, na 2 CO 3 The content of (C) is 1000mol/L,carrying out dehydration condensation reaction at 100 ℃, wherein the stirring speed is 100rpm during the reaction, and the reaction time is controlled to be 1h; after the reaction is finished, sequentially carrying out suction filtration and precipitation, centrifugal washing and freeze drying on the reaction product, wherein the specific steps are as follows: medium-speed filter paper is adopted in the suction filtration process, the vacuum degree is controlled to be-0.08 MPa, and ethanol is repeatedly used for flushing and suction filtration in the suction filtration process; the solid powder after suction filtration is redispersed in ethanol, and is settled for 1h, and the supernatant is removed; dispersing the solid powder after suction filtration and precipitation in deionized water, wherein the solid content of the solid powder in the deionized water is 10g/mL, and then placing the solid powder in a centrifugal machine for centrifugal washing, wherein the adopted centrifugal speed is 10000rpm, and the centrifugal time is 3min; and (3) after centrifugal washing for four times, placing the solid powder into a low-temperature dryer for freeze drying, wherein the freeze drying temperature is-75 ℃, and the freeze drying time is 96 hours, so as to obtain the retinoic acid/water magnesite composite powder.
Comparative example 1
Dissolving 0.5mol of retinoic acid in N, N dimethylformamide, and stirring at a speed of 600rpm at 35 ℃ for 80min to obtain a retinoic acid solution with a concentration of 0.5 mol/L; 1mol of the water magnesite powder is dispersed in N, N dimethylformamide, and stirred at a speed of 1000rpm for 120min at 40 ℃ to obtain a water magnesite solution with a concentration of 1 mol/L. Then dripping the water magnesite solution into the retinoic acid solution, wherein the dripping speed is 1 drop/3 s, and after the dripping is finished, dripping NaHCO with the concentration of 1L 3 Adding dispersion liquid into the mixed solution, wherein NaHCO 3 The dispersion liquid is prepared from NaHCO 3 And N, N dimethylformamide, na 2 CO 3 The content of (2) is 200mol/L, dehydration condensation reaction is carried out at 70 ℃, the stirring speed is 600rpm during the reaction, and the reaction time is controlled to be 18h; after the reaction is finished, sequentially carrying out suction filtration and precipitation, centrifugal washing and freeze drying on the reaction product, wherein the specific steps are as follows: the rapid filter paper is adopted in the suction filtration process, the vacuum degree is controlled to be-0.08 MPa, and ethanol is repeatedly used for washing and suction filtration in the suction filtration process; the solid powder after suction filtration is redispersed in ethanol, and is settled for 1h, and the supernatant is removed; dispersing the solid powder after suction filtration and precipitation in deionized water, wherein the solid powder is prepared byThe solid content in deionized water is 8g/mL, and then the deionized water is placed in a centrifugal machine for centrifugal washing, wherein the adopted centrifugal speed is 5000rpm, and the centrifugal time is 45min; and (3) after centrifugal washing for four times, placing the solid powder into a low-temperature dryer for freeze drying, wherein the freeze drying temperature is-25 ℃, and the freeze drying time is 72 hours, so as to obtain the retinoic acid/water magnesite composite powder.
Comparative example 2
120mol of retinoic acid is dissolved in N, N dimethylformamide and stirred at the speed of 600rpm for 100min at the temperature of 25 ℃ to obtain retinoic acid solution with the concentration of 400 mol/L; 2mol of the water magnesite powder is dispersed in N, N dimethylformamide, and stirred at the speed of 1100rpm for 150min at the temperature of 30 ℃ to obtain a water magnesite solution with the concentration of 2 mol/L. Then dripping the water magnesite solution into the retinoic acid solution, wherein the dripping speed is 1 drop/2 s, and after the dripping is finished, adding CaCO with the concentration of 2L 3 Adding the solution into the mixed solution, wherein CaCO 3 The dispersion liquid is prepared from CaCO 3 And N, N dimethylformamide, caCO 3 The content of (2) is 300mol/L, dehydration condensation reaction is carried out at 80 ℃, the stirring speed is 900rpm during the reaction, and the reaction time is controlled to be 16 hours; after the reaction is finished, sequentially carrying out suction filtration and precipitation, centrifugal washing and freeze drying on the reaction product, wherein the specific steps are as follows: the vacuum degree is controlled to be-0.085 MPa by adopting quick filter paper in the suction filtration process, and ethanol is repeatedly used for flushing and suction filtration in the suction filtration process; the solid powder after suction filtration is redispersed in ethanol, and is settled for 30 hours, and the supernatant is removed; dispersing the solid powder after suction filtration and precipitation in deionized water, wherein the solid content of the solid powder in the deionized water is 8g/mL, and then placing the solid powder in a centrifugal machine for centrifugal washing, wherein the adopted centrifugal speed is 3500rpm, and the centrifugal time is 55min; and (3) after centrifugal washing for four times, placing the solid powder into a low-temperature dryer for freeze drying, wherein the freeze drying temperature is-55 ℃, and the freeze drying time is 36 hours, so as to obtain the retinoic acid/water magnesite composite powder.
Performance test:
the retinoic acid/water magnesite composite powder prepared in examples 1 to 3 and comparative examples 1 to 2 was subjected to particle size, oil absorption value and specific surface area test, and the test results are shown in table 1.
The specific test method comprises the following steps: (1) particle diameter: measuring the particle size and distribution of the powder by a laser particle distribution measuring instrument; (2) oil absorption value: testing according to DB/T5211.15-2014 standard; (3) specific surface area: the specific surface area BET was used for the test.
TABLE 1 particle size, oil absorption and specific surface area test results
| Project | D 50 (μm) | Oil absorption value (mL/100 g) | Specific surface area (m) 2 /g) |
| Hydromagnesite | 2.8 | 60 | 10.02 |
| Example 1 | 1.67 | 29 | 17.85 |
| Example 2 | 1.69 | 30 | 17.62 |
| Example 3 | 1.71 | 31 | 17.34 |
| Comparative example 1 | 2.88 | 50 | 12.13 |
| Comparative example 2 | 3.03 | 45 | 11.10 |
From the test results in examples 1 to 3 in Table 1, it can be seen that: after the natural product retinoic acid with a certain proportion is added to modify the water magnesite, the median particle diameter D of the composite powder is that 50 The typical descending trend is shown, and the retinoic acid modified water magnesite can be mostly in a single particle dispersion state, which is possibly related to that retinoic acid can well shield hydroxyl groups on the surface of the water magnesite, so that the retinoic acid is in a hydrophobic state, and other acting forces such as hydrogen bonds do not exist between the retinoic acid and the hydroxyl groups, so that the agglomeration effect among the powder is effectively reduced. In contrast, when the surface retinoic acid is too small (molar ratio lower than 1:1, such as comparative example 1) or too high (molar ratio greater than 50:1, such as comparative example 2), the modifying effect on the hydromagnesite is in a reduced state, D 50 The value increases, indicating that a typical agglomeration phenomenon occurs; from the perspective of oil absorption value, the retinoic acid added with a proper proportion can obviously improve the oil absorption value of the water magnesite powder, so that the oil absorption value is reduced from original 60mL/100g to 29-31 mL/100g, which is possibly related to the hydrophobic structure of retinoic acid, the reduction of the oil absorption value can obviously improve the adsorption performance of the retinoic acid to auxiliary agents in the processing process, the cost is saved, the fluidity in the processing process is improved, the comprehensive performance is improved, and when the mole ratio of the retinoic acid added as a natural product to the water magnesite is too low or too high, the oil absorption value of the composite powder is improvedThe rising phenomenon still occurs, and the oil absorption value is still higher although the oil absorption value has a certain descending trend compared with the oil absorption value of the completely unmodified brucite powder, so that the comprehensive performance of the composite powder is not improved; after the retinoic acid natural product is modified according to a proper proportion, the specific surface area is greatly improved, the composite powder is likely to be dispersed, the median particle diameter is reduced, compared with the prior art, when the added amount of the retinoic acid natural product is too low or too high, the increase of the specific surface area is not obvious, the surface is likely to remain more hydroxyl groups due to the fact that the surface is relatively low as Huang Suanma mol, the aggregation is likely to occur, the median particle diameter is increased, the specific surface area is correspondingly reduced, and when the surface is relatively high as Huang Suanma mol, a plurality of water magnesite powder particles are likely to be wrapped together, so that the particle size is increased, and the specific surface area is also reduced. The result shows that the surface polarity of the natural water magnesite can be effectively improved by adding the natural product retinoic acid with proper proportion, which is beneficial to improving the comprehensive performance of the composite powder.
Spectroscopic testing of retinoic acid/water magnesite composite powder.
(1) Response test of retinoic acid/water magnesite composite powder in solutions with different viscosities:
solutions of different viscosities were prepared by adding glycerol to deionized water in different volume fractions, and retinoic acid/water-magnesite composite powder prepared in example 1 was added to the above solution, and allowed to stand at room temperature for a while, controlling the concentration of the added retinoic acid/water-magnesite composite powder to be 10 μm, wherein the excitation wavelength was 410nm, and the measured spectrum was shown in fig. 4. From the results, as the viscosity of the solution gradually increases, the intensity of the fluorescence signal obtained becomes more remarkable, which indicates that the composite powder has a better response effect on the viscosity, probably because a large amount of retinoic acid on the surface contains more conjugated structures capable of freely rotating, the conjugated single double bonds can freely rotate in the solution with low viscosity, the energy of an excited state is consumed by a mechanical dissipation mode, the free rotation is difficult in the solution with high viscosity, the energy of the excited state is dissipated by a radiation transition mode, and a strong fluorescence signal is released, and the overall response effect on the micro-region viscosity of the solution is improved by about 65 times (as shown in table 2). In addition, the retinoic acid/water magnesite composite powder prepared in example 1 was tested for its sensitivity coefficient to viscosity according to the present invention, as shown in fig. 5. The test result shows that the viscosity sensitivity coefficient of the composite powder is 1.93, and the composite powder has strong application potential on tackifying induction of correction fluid.
TABLE 2 optical Signal Strength of retinoic acid/Water magnesite composite powder in solution atmosphere with different viscosities
| Glycerol volume fraction | Fluorescence intensity |
| 0％ | 34.7 |
| 10％ | 153.6 |
| 30％ | 396.9 |
| 50％ | 668.6 |
| 70％ | 999.5 |
| 99％ | 2276.1 |
(2) Absorption spectrum diagram of retinoic acid/water magnesite composite powder in solvents of different polarities:
because of the multifunctional requirement, the correction fluid needs to be added with various solvents, and the signal stability of retinoic acid/water magnesite composite powder in various solvent systems is important. The retinoic acid/water magnesite composite powder prepared in example 1 was added to six common solvents of water, ethanol, tetrahydrofuran, dimethyl sulfoxide, toluene and glycerol respectively, the concentration of the retinoic acid/water magnesite composite powder was controlled to be 10 mu M, and the absorption spectrum of the retinoic acid/water magnesite composite powder in solvents with different polarities was tested, as shown in fig. 6, and the corresponding quantification results are shown in table 3. As can be seen from the test results, the absorption spectrum peak value of the retinoic acid/water magnesite composite powder in various solvents with different polarities (except glycerol) is basically around 356nm, the absorbance is similar, but in glycerol, the absorption spectrum peak value of the retinoic acid/water magnesite composite powder is red shifted to 396.5nm, and the absorbance is reduced to 0.49, so that the retinoic acid/water magnesite composite powder is suitable for being used in the solvents with different polarities, and has low dependence on the polarity of the solvents, and compared with the retinoic acid/water magnesite composite powder, the dependence on the viscosity is obvious, and particularly in high-viscosity solutions, the absorption spectrum change is obvious.
TABLE 3 absorption spectrum peak and absorbance of retinoic acid/water magnesite composite powder
(3) Light stability test of retinoic acid/water magnesite composite powder in high viscosity solution:
the retinoic acid/water-magnesite composite powder prepared in example 1 was dispersed in trichloroethane, and then added to a high viscosity solution (wherein the composition of the high viscosity solution is 99% of glycerol and 1% of deionized water, the viscosity value of the high viscosity solution is 956.0 cP), the mixing concentration of the retinoic acid/water-magnesite composite powder was controlled to be 10 mu mol/L, and the light stability of the retinoic acid/water-magnesite composite powder was tested by irradiation for 60min under an excitation light source of 365nm, and the result is shown in fig. 7. From the results, the retinoic acid/water magnesite composite powder can still release stronger optical signals under long-term irradiation, has excellent optical stability, is suitable for long-term existence in correction fluid and can exert efficacy.
(4) Application of retinoic acid/water magnesite composite powder in correction fluids with different viscosities:
specifically, the retinoic acid/water magnesite composite powder prepared in example 1 was dispersed in 3 different correction fluids (correction fluid 1, correction fluid 2 and correction fluid 3), wherein the mixing concentration of retinoic acid/water magnesite composite powder was controlled to be 1 μmol/L, and the luminescence intensity was observed, and the result is shown in fig. 8. As can be seen from fig. 8, there is a difference in the viscosity of the three correction fluids, in which the viscosity of correction fluid 1 is 1.83cP, the viscosity of correction fluid 2 is 2.42cP, and the viscosity of correction fluid 3 is 3.60cP, and when retinoic acid/water magnesite composite powder is added to the correction fluid, there is a significant difference in the optical signal intensity, and the signal intensity is also increased with the increase in the viscosity, and the specific values are shown in table 4. The result shows that the retinoic acid/water magnesite composite powder has better response effect on correction fluids with different viscosities, namely, has positive correlation with the viscosities, and can sense the change of the viscosities through the intensity of optical signals, thus the composite powder can provide the possibility of visual observation for the preparation process and the thinness of the correction fluids.
TABLE 4 optical signal intensity of retinoic acid/water magnesite composite powder in correction fluids with different viscosities
| Correction fluid type | Fluorescence intensity | Viscosity of the mixture |
| Correction fluid 1 | 159.3 | 1.83 |
| Correction fluid 2 | 198.6 | 2.42 |
| Correction fluid 3 | 399.5 | 3.60 |
According to the invention, the retinoic acid which is a natural product is combined with the water magnesite widely existing in the nature to prepare the retinoic acid/water magnesite composite powder, the rotatability of a large conjugated structure of the retinoic acid is fully utilized to realize the response imaging on the viscosity of a correction fluid micro-area, and the basic magnesium carbonate characteristic of the water magnesite is utilized to realize the smoke suppression and flame retardance effects, meanwhile, the retinoic acid can reduce the surface polarity of the natural water magnesite, improve the compatibility of the retinoic acid in a polymer matrix and greatly reduce the oil absorption value of the natural water magnesite, and is a natural char former which can form a synergistic effect with the internal natural water magnesite, so that the retinoic acid has great advantages in improving the comprehensive performance of the composite powder; in addition, the whiteness value of the natural water magnesite reaches 96.0, has better covering power, and can meet the correction effect of correction fluid; finally, the retinoic acid/water magnesite composite powder is prepared by adopting a one-step method, and the main raw materials are all from nature, belong to typical natural products, are very environment-friendly, are suitable for large-scale preparation and application, not only can the traditional natural stone ore be high-valued, but also the mutual combination of a plurality of natural products can be realized so as to jointly improve the comprehensive performance of the inorganic powder.
As can be seen from the above examples, the present invention provides a retinoic acid/water magnesite composite powder, a preparation method and an application thereof, wherein the retinoic acid/water magnesite composite powder of the present invention comprises retinoic acid and water magnesite, wherein retinoic acid is the shell of the composite powder, water magnesite is the inner core of the composite powder, and the molar ratio of retinoic acid to water magnesite is 1-50:1. The retinoic acid/water magnesite composite powder is prepared by sequentially mixing a water magnesite solution and a dehydrating agent dispersion liquid with a retinoic acid solution, and then carrying out dehydration condensation reaction. The retinoic acid/water magnesite composite powder has a retinoic acid layer on the surface, has a flexible conjugated structure, can release weak light signals in low-viscosity correction fluid and release strong light signals in high-viscosity correction fluid, and is beneficial to the formula design of the correction fluid. And the conjugated structure of retinoic acid can lead the retinoic acid to be very easy to form carbon in the combustion process, and has better synergistic flame retardant effect with the internal water magnesite.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The retinoic acid/water magnesite composite powder is characterized by comprising retinoic acid and water magnesite, wherein the retinoic acid is an outer shell of the composite powder, and the water magnesite is an inner core of the composite powder; the mol ratio of the retinoic acid to the water magnesite is 1-50:1.
2. The retinoic acid/water-magnesite composite powder according to claim 1, wherein D of the retinoic acid/water-magnesite composite powder 50 0.9-3.0 μm, wherein D of the core 50 0.8-2.8 mu m.
3. The method for preparing retinoic acid/water magnesite composite powder as defined in claim 1 or 2, which is characterized by comprising the following steps: sequentially mixing the water magnesite solution and the dehydrating agent dispersion liquid with the retinoic acid solution, and then carrying out dehydration condensation reaction to obtain retinoic acid/water magnesite composite powder.
4. The method according to claim 3, wherein the retinoic acid solution is prepared by mixing retinoic acid and a solvent; the water magnesite solution is formed by mixing water magnesite and a solvent; the dehydrating agent dispersion liquid is formed by mixing a dehydrating agent and a solvent; the solvent independently comprises one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, water and ethyl acetate.
5. The method according to claim 4, wherein the retinoic acid solution has a concentration of 1 to 500mol/L; the concentration of the water magnesite solution is 1-4 mol/L; the content of the dehydrating agent in the dehydrating agent dispersion liquid is 1-1000 mol/L.
6. The method according to claim 4 or 5, wherein the dehydrating agent comprises K 2 CO 3 、Cs 2 CO 3 、CaCO 3 、Na 2 CO 3 、NaHCO 3 And Ca (OH) 2 One of the following;
the molar ratio of the dehydrating agent to the water magnesite is 1-1000: 1.
7. the process according to claim 6, wherein the dehydration condensation reaction is carried out at a temperature of 45 to 100℃for a period of 1 to 60 hours.
8. The production method according to claim 3 or 4 or 5 or 7, wherein the product of the dehydration condensation reaction is sequentially subjected to suction filtration precipitation, centrifugal washing and freeze-drying; the freeze drying temperature is-70 to-5 ℃, and the freeze drying time is 1 to 96 hours.
9. The use of the retinoic acid/water-magnesite composite powder as defined in claim 1 or 2 in correction fluid, wherein the retinoic acid/water-magnesite composite powder and the correction fluid are mixed.
10. The use according to claim 9, wherein the retinoic acid/water magnesite composite powder has a mixing concentration of 0.1-20 μmol/L.
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| CN102417754A (en) * | 2011-11-28 | 2012-04-18 | 浙江大学宁波理工学院 | Water-based altering agent and preparation method thereof |
| CN104640569A (en) * | 2012-09-18 | 2015-05-20 | 默克专利股份有限公司 | Magnesium hydroxide carbonate as carrier material in active ingredient-containing preparations |
| CN113767153A (en) * | 2019-05-03 | 2021-12-07 | 欧米亚国际集团 | Surface-reacted magnesium carbonate as a carrier material for the release of one or more active agents in home care formulations |
| CN113149880A (en) * | 2021-04-24 | 2021-07-23 | 苏州铭开生物医药技术有限公司 | Preparation method of hydroxy pinacolone retinoic acid ester |
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