CN115703642A - Molecular sieve/mesoporous silica composite microsphere material, preparation method and loudspeaker - Google Patents
Molecular sieve/mesoporous silica composite microsphere material, preparation method and loudspeaker Download PDFInfo
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- CN115703642A CN115703642A CN202110890009.4A CN202110890009A CN115703642A CN 115703642 A CN115703642 A CN 115703642A CN 202110890009 A CN202110890009 A CN 202110890009A CN 115703642 A CN115703642 A CN 115703642A
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- molecular sieve
- mesoporous silica
- silica composite
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 132
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000004005 microsphere Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000005469 granulation Methods 0.000 claims abstract description 16
- 230000003179 granulation Effects 0.000 claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims description 41
- 239000012043 crude product Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 239000012798 spherical particle Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910016287 MxOy Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 230000006872 improvement Effects 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 3
- 239000012855 volatile organic compound Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 6
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 6
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- WPMWEFXCIYCJSA-UHFFFAOYSA-N Tetraethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCO WPMWEFXCIYCJSA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
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- -1 polyoxyethylene lauryl ether Polymers 0.000 description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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Images
Abstract
The invention relates to a molecular sieve/mesoporous silica composite microsphere material, a preparation method and a loudspeaker, belonging to the technical field of material preparation. According to the invention, by combining the synthesis process of mesoporous silica and directly adding MWW molecular sieve in the synthesis process of massive silica, the massive molecular sieve/mesoporous silica composite material is formed, and the MWW molecular sieve has strong tunnel structure plasticity, so that the tunnel and the outer surface can be enlarged and exposed, and the acoustic performance can be prevented from being damaged by adding a binder. In addition, the molecular sieve/mesoporous silica composite microsphere material which has obviously increased air absorption and desorption capacity at normal temperature and obviously reduced release amount of volatile organic compounds is obtained by spray granulation, so that the molecular sieve/mesoporous silica composite microsphere material prepared by the method has better low-frequency improvement performance.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a molecular sieve/mesoporous silicon dioxide composite microsphere material, a preparation method and a loudspeaker.
Background
With the development of science and technology and the improvement of living standard, people have higher performance requirements on the loudspeaker. In particular, for portable electronic devices, it is required to provide excellent acoustic performance while being as small in volume as possible. The sound quality of the loudspeaker is closely related to the design and manufacturing process, and particularly the size design of the rear cavity of the loudspeaker. In general, the smaller the speaker back cavity is, the poorer the acoustic response in the low frequency band and the poorer the acoustic performance such as sound quality, so it is necessary to enlarge the back cavity of the speaker to improve the acoustic response in the low frequency band.
In the prior art, sound absorption materials such as porous carbon, silicon dioxide and molecular sieves are usually filled in a rear cavity of a loudspeaker box so as to increase the virtual volume of the rear cavity and improve the gas sound compliance of the rear cavity, thereby improving the low-frequency performance. Among them, the highly hydrophobic high-silicon molecular sieve has the best effect of improving low-frequency performance.
In the prior art, molecular sieves with structures of FER, MFI, BEA and MEL are mostly adopted. Generally, the molecular sieve is powder with 10 nm-10 μm, and because of the design limitation of the loudspeaker, the powder is difficult to directly fill in the rear box, and the powder needs to be prepared into particles with larger size through a forming process so as to be applied to the loudspeaker. Most of the existing forming processes are forming by means of spray granulation, extrusion granulation and the like after mixing molecular sieve powder and a binder, however, the addition of the binder can block micropores on the surface of the molecular sieve and damage the low-frequency response of the molecular sieve. In the subsequent working process, organic molecules volatilized from the organic adhesive occupy adsorption sites in pore channels of the molecular sieve, so that the adsorption effect on air is weakened, and the low-frequency response of the molecular sieve is influenced again.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide a molecular sieve/mesoporous silica composite microsphere material, a method for producing the same, and a speaker.
The invention provides a preparation method of a molecular sieve/mesoporous silica composite microsphere material, which is characterized by comprising the following steps: step 1, stirring and heating a solution containing a surfactant to a certain temperature to obtain a solution A; step 2, adding a silicon source into the solution A, and stirring to obtain a mixed solution B; step 3, adding an MWW molecular sieve into the mixed solution B, and stirring to obtain a mixed solution C; step 4, filtering the mixed solution C, and washing the solid to obtain a crude product; step 5, carrying out spray granulation or extrusion granulation on the crude product to obtain spherical particles; and step 6, calcining the spherical particles to obtain the molecular sieve/mesoporous silica composite microsphere material.
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention also has the following characteristics: wherein the mass ratio of the surfactant to the deionized water in the solution A is (0.5-2.5): 60.
the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention is also characterized in that: wherein the silicon source is one or more of tetraethyl orthosilicate, tetrabutyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, water glass and white carbon black.
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention also has the following characteristics: wherein the mass of the surfactant and the silicon source is 1: (3-5).
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention is also characterized in that: wherein the mass ratio of the MWW molecular sieve to the silicon source is (0.4-4): 1.
the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention is also characterized in that: wherein the surfactant is any one or more of long-chain primary amine cationic surfactant, long-chain quaternary ammonium salt cationic surfactant, multi-head quaternary ammonium salt cationic surfactant, polyethylene oxide nonionic surfactant, amphiphilic block copolymer nonionic surfactant (such as PEO-PPO-PEO) or sorbitol nonionic surfactant, and preferably polyethylene oxide nonionic surfactant.
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention is also characterized in that: wherein the solution A further comprises a polycondensation catalyst.
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention also has the following characteristics: wherein, the polycondensation catalyst is one or more of protonic acid, alkali or fluoride.
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention is also characterized in that: wherein the MWW molecular sieve comprises a framework and framework external cations, and the framework comprises SiO 2 A nonmetal or metal oxide MxOy, the atomic ratio of Si/M in the skeleton is more than 20, wherein M is at least one of aluminum, titanium, boron, iron, gallium, chromium, zirconium or germanium; the extra-framework cation is at least one of a hydrogen ion, an alkali metal ion or an alkaline earth metal, and the Si/M atomic ratio of the framework of the MWW molecular sieve is preferably greater than 50.
In the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention, the preparation method can also have the following characteristics: wherein, the MWW molecular sieve has rich pore channel structures inside, most of the pore channel structures are nano-scale micropores and mesopores, and the particle size of the MWW molecular sieve is 10-1000nm.
In the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention, the preparation method can also have the following characteristics: wherein, the particle size of the molecular sieve/mesoporous silicon dioxide composite microsphere is distributed between 100 and 800 μm, preferably between 200 and 400 μm.
In the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention, the preparation method can also have the following characteristics: wherein, the shape of the mesoporous silicon dioxide is blocky.
In the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the invention, the preparation method can also have the following characteristics: the mesoporous silica is one or more of mesoporous silica synthesized by using a cationic surfactant or a nonionic surfactant as a template agent, and is preferably MSU mesoporous silica.
The invention provides a molecular sieve/mesoporous silica composite microsphere material which has the characteristics and is prepared by any one of the preparation methods of the molecular sieve/mesoporous silica composite microsphere material.
The invention provides a loudspeaker, which is characterized in that the rear cavity filler of the loudspeaker adopts the molecular sieve/mesoporous silica composite microsphere material.
Action and effects of the invention
According to the preparation method of the molecular sieve/mesoporous silica composite microsphere material, the MWW molecular sieve is directly added in the synthesis process of the massive silicon dioxide to form the massive molecular sieve/mesoporous silica composite material by combining the synthesis process of the mesoporous silica, and the MWW molecular sieve has strong pore structure plasticity and can enlarge and expose the pore and the outer surface, so that the acoustic performance can be prevented from being damaged by adding a binder. In addition, the molecular sieve/mesoporous silica composite microsphere material which has obviously increased air absorption and desorption capacity at normal temperature and obviously reduced release amount of volatile organic compounds is obtained by spray granulation, so that the molecular sieve/mesoporous silica composite microsphere material prepared by the method has better low-frequency improvement performance.
Drawings
FIG. 1 is a schematic diagram illustrating the steps of a method for preparing a molecular sieve/mesoporous silica composite microsphere material according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction pattern of the MWW molecular sieve/mesoporous silica composite microsphere material in example 1 of the present invention;
fig. 3 is a nitrogen adsorption-desorption isotherm in example 2 of the present invention;
FIG. 4 is a DFT pore size distribution curve in example 3 of the present invention;
fig. 5 is a sound pressure frequency response curve in embodiment 4 of the present invention; and
FIG. 6 is an optical microscope photograph in example 5 of the present invention;
figure 7 is a plot of the micropore size distribution of a binder-added shaped MWW molecular sieve material of the comparative example of the present invention.
Detailed Description
The technical means, creation characteristics, achievement purposes and effects of the invention are easy to realize
It is understood that the molecular sieve/mesoporous silica composite microsphere material, the preparation method and the speaker of the present invention are specifically described below with reference to the following examples and accompanying drawings.
< example 1>
Fig. 1 is a schematic step diagram of a method for preparing a molecular sieve/mesoporous silica composite microsphere material according to an embodiment of the present invention.
As shown in fig. 1, the preparation method of the molecular sieve/mesoporous silica composite microsphere material provided in this embodiment includes the following steps:
step 1, stirring and heating a solution containing a surfactant to a certain temperature to obtain a solution A.
And 2, adding a silicon source into the solution A, and stirring to obtain a mixed solution B.
And 3, adding the MWW molecular sieve into the mixed solution B, and stirring and aging to obtain a mixed solution C.
And 4, carrying out suction filtration on the mixed solution C, and washing the solid to obtain a crude product.
And 5, carrying out spray granulation or extrusion granulation on the crude product to obtain spherical particles.
And 6, calcining the spherical particles to obtain the molecular sieve/mesoporous silica composite microsphere material.
In this embodiment, the preparation method of the molecular sieve/mesoporous silica composite microsphere material specifically includes the following steps:
step 1, weighing 2.47g Brij30 (polyoxyethylene lauryl ether) and 0.05g ammonium fluoride, adding into 120g deionized water, adding 6.56ml cyclohexane, stirring in a water bath at 60 ℃ until Brij30 (namely surfactant) is dissolved, and obtaining mixed liquid A.
And 2, under the stirring condition, after the mixed solution A is clear and transparent, dropwise adding 10ml TEOS (tetraethyl orthosilicate) into the mixed solution A, and then continuously stirring at room temperature for 30min to obtain a mixed solution B.
Step 3, under the stirring condition, adding 5g of MWW molecular sieve (which is purchased from Tide New materials Co., ltd., zhejiang province, with layered and cage structure titanium borosilicate, lamellar crystal particles with the size of 0.5-5 μm, silicon-titanium ratio of about 40 and silicon-boron ratio of about 120) into the mixed solution B, wherein the mass ratio of the raw materials of the final mixed system is as follows: brij30 4 F:MWW:H 2 O =123.5: 186, wherein the stirring speed of the solution was controlled to 550rpm, and the solution was aged with stirring at room temperature for 48 hours to obtain a mixed solution C.
And 4, carrying out suction filtration on the mixed solution C, taking the solid, and washing to obtain a crude product.
And 5, adding water into the crude product to dilute the crude product until the crude product has certain fluidity, putting the crude product into a spray granulator, and atomizing and drying the crude product to obtain spherical particles.
And 6, roasting the sample subjected to spray granulation in a muffle furnace at 550 ℃ for 6 hours, and removing the template agent to obtain the MWW molecular sieve/MSU mesoporous silica composite microsphere material with the mass ratio of the molecular sieve to the mesoporous silica being 2.
Fig. 2 is an X-ray diffraction spectrum of the MWW molecular sieve/mesoporous silica composite microsphere material in example 1 of the present invention.
As shown in fig. 2, the characteristic peak of the X-ray diffraction pattern of the MWW molecular sieve/mesoporous silica composite microsphere material prepared in this example matches with the characteristic peak of the MWW molecular sieve of the standard card, indicating that the molecular sieve conforms to the MWW structural characteristics.
< example 2>
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the embodiment is similar to that of the embodiment 1, and comprises the following specific steps:
step 1, weighing 3.81g of Tetradecylamine (Tetradecamine) and 16.56g of absolute ethyl alcohol (Ethanol) and adding into 120g of deionized water, and stirring in a water bath at 60 ℃ until the Tetradecylamine (namely a surfactant) is dissolved to obtain a mixed solution A.
And 2, under the stirring condition, after the mixed solution A is clear and transparent, dropwise adding 10ml of TEOS (tetraethyl orthosilicate) into the mixed solution A, and then continuously stirring for 30min at room temperature to obtain a mixed solution B.
Step 3, under the stirring condition, adding 5g of MWW molecular sieve (which is purchased from titanium borosilicate of a layered structure and a cage structure, purchased from Taede New materials Co., ltd., zhejiang province, the size of the laminar borosilicate is 0.5-5 μm, the silicon-titanium ratio is about 40, and the silicon-boron ratio is about 120) into the mixed solution B, wherein the molar ratio of the raw materials of the final mixed system is as follows: tetradecylamine, ethanol: TEOS: MWW: H 2 O =1: 20.14.
And 4, filtering the mixed solution C, taking the solid, and washing to obtain a crude product.
And 5, adding water into the crude product to dilute the crude product until the crude product has certain fluidity, putting the crude product into a spray granulator, and atomizing and drying the crude product to obtain spherical particles.
And 6, roasting the sample subjected to spray granulation for 6 hours at 550 ℃ in a muffle furnace, and removing the template agent to obtain the MWW molecular sieve/HMS mesoporous silica composite microsphere material with the mass ratio of the MWW molecular sieve to the mesoporous silica being 1.
Fig. 3 is a nitrogen adsorption-desorption isotherm of the molecular sieve/mesoporous silica composite microsphere material obtained in example 2.
As shown in FIG. 3, the total pore volume and the total specific surface area of the molecular sieve/mesoporous silica composite microsphere material are respectively 0.813cc/g and 716.747 m, which can be obtained from the nitrogen adsorption-desorption isotherm 2 The/g shows that the molecular sieve/mesoporous silica composite microsphere material has rich pore structure and large specific surface area, can adsorb a large amount of gas molecules on the surface of the molecular sieve/mesoporous silica composite microsphere material, and achieves the effect of increasing the volume of the virtual back cavity by utilizing the adsorption-desorption effect of the gas molecules.
< example 3>
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the embodiment is similar to that of the embodiment 1, and comprises the following specific steps:
step 1, weighing 3.81g of tetradecylamine and 16.56g of absolute ethyl alcohol, adding into 120g of deionized water, and stirring at room temperature until the tetradecylamine (namely, a surfactant) is dissolved to obtain a mixed solution A.
And 2, dropwise adding 10ml TEOS (tetraethyl orthosilicate) under the stirring condition after the solution is clear and transparent, and then continuously stirring for 30min at room temperature to obtain a mixed solution B.
Step 3, under the stirring condition, adding 5g of MWW molecular sieve (which is purchased from Tide New materials Co., ltd., zhejiang province, and has a layered and cage structure, titanium borosilicate with the size of 0.5-5 μm sheet crystal particles, the silicon-titanium ratio of about 40 and the silicon-boron ratio of about 120) into the mixed solution, wherein the final mixed system comprises the following raw materials in percentage by mass: tetradecylamine, ethanol: TEOS: MWW: H 2 O =1: 4.35, 2.44.
And 4, carrying out suction filtration on the mixed solution C, taking the solid, and washing to obtain a crude product.
And 5, adding water into the crude product to dilute the crude product until the crude product has certain fluidity, putting the crude product into a spray granulator, and atomizing and drying the crude product to obtain spherical particles.
And 6, roasting the sample subjected to spray granulation for 6 hours at 550 ℃ in a muffle furnace, and removing the template agent to obtain the MWW molecular sieve/HMS mesoporous silica composite microsphere material with the mass ratio of the molecular sieve to the mesoporous silica being 2.
Fig. 4 is a DFT pore size distribution curve of the molecular sieve/mesoporous silica composite microsphere material obtained in this example 3.
As shown in fig. 4, it can be obtained from the DFT aperture distribution diagram that the pore diameters of the molecular sieve/mesoporous silica composite microsphere material obtained in this embodiment are mainly concentrated near 1.2nm, and the pore diameters of the mesopores are mainly distributed near 5-20nm, which indicates that the molecular sieve/mesoporous silica microsphere material not only has rich micropore channels, but also can adsorb a large amount of gas molecules, and has rich mesopore channels, which is beneficial to the mass transfer and diffusion of the gas molecules in the molecular sieve microsphere.
< example 4>
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the embodiment is similar to that of the embodiment 1, and comprises the following specific steps:
step 1, weighing 2.47g Brij30 (polyoxyethylene lauryl ether) and 0.08g ammonium fluoride, adding into 120g deionized water, then adding 5ml cyclohexane, stirring in a water bath at 60 ℃ until Brij30 (namely a surfactant) is dissolved, and obtaining mixed liquid A.
And 2, under the stirring condition, after the mixed solution A is clear and transparent, dropwise adding 10ml of TEOS (tetraethyl orthosilicate) into the mixed solution A, and then continuously stirring for 30min at room temperature to obtain mixed solution B.
Step 3, under the condition of stirring, adding 8g of MWW molecular sieve (purchased from Tide New Material Co., ltd., zhejiang, layered and cage-like structures, titanium borosilicate with the size of 0.5-5 μm, flaky crystal particles with the silicon-titanium ratio of about 40 and silicon-boron ratio of about 120) into the mixed solution B, wherein the final mixed system comprises the following raw materials in percentage by mass: brij30 4 F:MWW:H 2 O = 123.5.
And 4, carrying out suction filtration on the mixed solution C, taking the solid, and washing to obtain a crude product.
And 5, adding water into the crude product to dilute the crude product until the crude product has certain fluidity, putting the crude product into a spray granulator, and atomizing and drying the crude product to obtain spherical particles.
And 6, roasting the sample subjected to spray granulation in a muffle furnace at 550 ℃ for 6 hours, and removing the template agent to obtain the MWW molecular sieve/MSU mesoporous silica composite microsphere material with the mass ratio of the molecular sieve to the mesoporous silica being 3.
Fig. 5 is an acoustic pressure frequency response curve of the molecular sieve/mesoporous silica composite microsphere material obtained in example 4.
As shown in fig. 5, it can be seen from the sound pressure frequency response curve that after the molecular sieve/mesoporous silica composite microsphere material obtained in this embodiment is filled, the resonance frequency of the speaker system is reduced from 897.79Hz to 609.34Hz, and the resonance frequency deviation is as high as 288.45Hz, which indicates that the molecular sieve/mesoporous silica composite microsphere material can achieve the purpose of increasing the virtual back cavity of the speaker system, and can greatly improve the low frequency responsiveness of the speaker system, and has an excellent application prospect.
< example 5>
The preparation method of the molecular sieve/mesoporous silica composite microsphere material provided by the embodiment is similar to that of the embodiment 1, and comprises the following specific steps:
step 1, weighing 2.47g Brij30 (polyoxyethylene lauryl ether) and 0.08g ammonium fluoride, adding into 120g deionized water, adding 5ml cyclohexane, stirring in a water bath at 60 ℃ until Brij30 (namely surfactant) is dissolved, and obtaining mixed solution A.
And 2, under the stirring condition, after the mixed solution A is clear and transparent, dropwise adding 10ml of TEOS (tetraethyl orthosilicate) into the mixed solution A, and then continuously stirring for 30min at room temperature to obtain mixed solution B.
Step 3, under the stirring condition, adding 5g of MWW molecular sieve (purchased from Tide New Material Co., ltd., zhejiang, layered and cage-like structures, titanium borosilicate with the size of 0.5-5 μm, flaky crystal particles with the silicon-titanium ratio of about 40 and silicon-boron ratio of about 120) into the mixed solution B, wherein the final mixed system comprises the following raw materials in percentage by mass: brij30 TEOS: NH 4 F:MWW:H 2 O = 123.5.
And 4, carrying out suction filtration on the mixed solution C, taking the solid, and washing to obtain a crude product.
And 5, adding water to dilute the crude product until the crude product has certain fluidity, putting the crude product into a granulator, and atomizing and drying the crude product to obtain spherical particles.
And 6, roasting the sample subjected to spray granulation for 6 hours at 550 ℃ in a muffle furnace, and removing the template agent to obtain the MWW molecular sieve/MSU mesoporous silica composite microsphere material with the mass ratio of the molecular sieve to the mesoporous silica being about 2.
FIG. 6 is an optical microscope photograph of the molecular sieve/mesoporous silica composite microsphere material obtained in example 5.
As shown in fig. 6, it can be seen from the optical microscope photograph that the molecular sieve/mesoporous silica composite microsphere material obtained in this embodiment has uniform morphology, smooth surface, high particle sphericity, and particle size distribution centered at 200-350 μm, which indicates that the particles of the molecular sieve/mesoporous silica composite microsphere material meet the requirements of a speaker system, and the smooth spherical morphology of the surface enables the molecular sieve/mesoporous silica composite microsphere material to be tightly packed during the filling process, and the performance of the molecular sieve/mesoporous silica composite microsphere material is not affected by debris generated due to asymmetric morphology during the working process.
< comparative example >
The comparative example provides a preparation method of MWW molecular sieve material formed by adding adhesive, which comprises the following steps:
step 1, 0.19g of cetyltrimethylammonium bromide (CTAB) was added to 5.25g of deionized water, and dissolved by appropriate heating to give a solution A.
And 2, adding 0.1g of 50wt% polyacrylic acid aqueous solution and 0.1g of styrene-acrylic emulsion into the solution A, and stirring for 30 minutes to obtain a mixed solution B.
And 3, adding 3.5g of MWW molecular sieve (purchased from Tide New materials Co., ltd., zhejiang, layered and cage-structured titanium borosilicate, flaky crystal particles with the size of 0.5-5 mu m, silicon-titanium ratio of about 40 and silicon-boron ratio of about 120) into the mixed solution B, and stirring for 30 minutes to obtain uniform and stable slurry.
And 4, adding water into the slurry to dilute the slurry to have certain fluidity, putting the slurry into a granulator, and atomizing and drying the slurry to obtain spherical particles.
And 5, roasting the spherical particles to obtain the MWW molecular sieve material formed by adding the adhesive.
As shown in FIG. 7, the MWW molecular sieve material formed by adding the binder has a micropore size distribution concentrated at 1.2nm and a mesopore size distribution of 7-12nm.
< test example >
Low frequency sound absorption test
The test method comprises the following steps: the molecular sieve/mesoporous silica composite microsphere materials obtained in examples 1 to 5 and the MWW molecular sieve material obtained in the comparative example and molded by adding an adhesive were filled as a low-frequency sound absorbing material in a rear cavity of a test speaker provided by austin science and technology (zhenjiang) ltd, and then the rear cover was closed and screwed down by four hexagonal screws, the device was turned over, and a connector clip was used to connect the speaker device with a reyson new spectrum multichannel test integrated system, to test the performance thereof and to collect data.
The test results are shown in table 1.
TABLE 1 Acoustic Property test results
As can be seen from table 1, when the molecular sieve/mesoporous silica composite microsphere material prepared in example 1 is used as a filler, the resonance frequency of the speaker can be lowered to 297.36Hz; and when the filling material is MWW molecular sieve material formed by adding adhesive, the resonance frequency of the loudspeaker is only reduced by 160.66Hz. The following conclusions can be drawn from the percentage reduction in the resonance frequency of the loudspeaker during the test: the molecular sieve/mesoporous silica composite microsphere material has better low-frequency sound absorption performance than a molecular sieve material formed by adding an adhesive.
Effects and effects of the embodiments
According to the method for preparing the molecular sieve/mesoporous silica composite microsphere material in this embodiment, the MWW molecular sieve is directly added in the synthesis process of the bulk silica, so as to form the bulk molecular sieve/mesoporous silica composite material. Because the MWW molecular sieve has a strong plasticity of the pore structure, the pore and the outer surface can be enlarged and exposed, and the acoustic performance can be prevented from being damaged by adding the binder. In addition, the molecular sieve/mesoporous silicon dioxide composite microsphere material which is obtained by spray granulation and has the advantages of obviously increased air absorption and desorption at normal temperature and obviously reduced release amount of volatile organic compounds has better low-frequency improvement performance.
Further, compared with the molecular sieve with the structure of FER, MFI, BEA, and MEL, the MWW molecular sieve provided in this example has a strong plasticity of the pore structure, and can increase and expose the pore and the outer surface by using the interlayer stripping, pillaring, and molecular level silanization reaming techniques, so as to meet different performance requirements. In addition, because the MWW molecular sieve has 2 independent 10-membered oxygen ring pore channels, one of which contains a supercage of 12-membered oxygen ring (0.71 nm × 1.81 nm), bowl-shaped cavities with inlets of 12-membered oxygen ring are provided on the surface of the crystal. Therefore, the molecular sieve not only has a unique structure, but also has the advantages of strong plasticity and modifiability due to the fact that the molecular sieve is derived from a layered precursor.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A preparation method of a molecular sieve/mesoporous silica composite microsphere material is characterized by comprising the following steps:
step 1, stirring and heating a solution containing a surfactant to a certain temperature to obtain a solution A;
step 2, adding a silicon source into the solution A, and stirring to obtain a mixed solution B;
step 3, adding an MWW molecular sieve into the mixed solution B, and stirring to obtain a mixed solution C;
step 4, filtering the mixed solution C, and washing a solid to obtain a crude product;
step 5, carrying out spray granulation or extrusion granulation on the crude product to obtain spherical particles; and
and 6, calcining the spherical particles to obtain the molecular sieve/mesoporous silica composite microsphere material.
2. The preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
wherein the mass ratio of the surfactant to the deionized water in the solution A is (0.5-2.5): 60.
3. the preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
wherein the silicon source is any one or more of tetraethyl orthosilicate, tetrabutyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, water glass and white carbon black.
4. The preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, wherein the preparation method comprises the following steps:
wherein the mass of the surfactant and the silicon source is 1: (3-5).
5. The preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
wherein the mass ratio of the MWW molecular sieve to the silicon source is (0.4-4): 1.
6. the preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
the surfactant is any one or more of long-chain primary amine cationic surfactant, long-chain quaternary ammonium salt cationic surfactant, multi-head quaternary ammonium salt cationic surfactant, polyethylene oxide nonionic surfactant, amphiphilic block copolymer nonionic surfactant or sorbitol nonionic surfactant.
7. The preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
wherein the solution A further comprises a polycondensation catalyst.
8. The preparation method of the molecular sieve/mesoporous silica composite microsphere material according to claim 1, which is characterized in that:
wherein the MWW molecular sieve comprises a framework and framework cations,
the skeleton bagSiO is included 2 A non-metal or metal oxide MxOy, the atomic ratio of Si/M in the framework is more than 20, wherein M is at least one of aluminum, titanium, boron, iron, gallium, chromium, zirconium or germanium;
the external skeleton cation is at least one of hydrogen ion, alkali metal ion or alkaline earth metal.
9. A molecular sieve/mesoporous silica composite microsphere material, which is characterized by being prepared by the preparation method of the molecular sieve/mesoporous silica composite microsphere material according to any one of claims 1 to 8.
10. A loudspeaker, characterized in that the filler of the back cavity of the loudspeaker adopts the molecular sieve/mesoporous silica composite microsphere material of claim 9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010043901A1 (en) * | 2000-04-13 | 2001-11-22 | Board Of Trustees Operating Michigan State Univ. | Process for the preparation of molecular sieve silicas |
| CN106792387A (en) * | 2016-12-13 | 2017-05-31 | 瑞声科技（南京）有限公司 | A kind of loudspeaker of sound-absorbing material and its preparation method and application the sound-absorbing material |
-
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- 2021-08-04 CN CN202110890009.4A patent/CN115703642A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010043901A1 (en) * | 2000-04-13 | 2001-11-22 | Board Of Trustees Operating Michigan State Univ. | Process for the preparation of molecular sieve silicas |
| CN106792387A (en) * | 2016-12-13 | 2017-05-31 | 瑞声科技（南京）有限公司 | A kind of loudspeaker of sound-absorbing material and its preparation method and application the sound-absorbing material |
Non-Patent Citations (1)
| Title |
|---|
| 孙博，郭勇，徐乐，黄哲昊，吴鹏，车顺爱: "微乳液法合成沸石/介孔二氧化硅复合微球", 《化学学报》, vol. 70, pages 2419 - 2424 * |
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