CN115744928A - Preparation method of tannic acid modified montmorillonite - Google Patents
Preparation method of tannic acid modified montmorillonite Download PDFInfo
- Publication number
- CN115744928A CN115744928A CN202211280215.4A CN202211280215A CN115744928A CN 115744928 A CN115744928 A CN 115744928A CN 202211280215 A CN202211280215 A CN 202211280215A CN 115744928 A CN115744928 A CN 115744928A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- tannic acid
- modified
- tannin
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 title claims description 148
- 239000001263 FEMA 3042 Substances 0.000 title claims description 148
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 title claims description 148
- 229940033123 tannic acid Drugs 0.000 title claims description 148
- 235000015523 tannic acid Nutrition 0.000 title claims description 148
- 229920002258 tannic acid Polymers 0.000 title claims description 148
- -1 tannic acid modified montmorillonite Chemical class 0.000 title claims description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 241
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 195
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920001864 tannin Polymers 0.000 claims abstract description 37
- 239000001648 tannin Substances 0.000 claims abstract description 37
- 235000018553 tannin Nutrition 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 17
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 116
- 230000009471 action Effects 0.000 claims description 37
- 239000000725 suspension Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000010907 mechanical stirring Methods 0.000 claims description 30
- 238000003760 magnetic stirring Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000005341 cation exchange Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 41
- 239000002994 raw material Substances 0.000 abstract description 27
- 235000013824 polyphenols Nutrition 0.000 abstract description 22
- 239000002131 composite material Substances 0.000 abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000008103 glucose Substances 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229910017059 organic montmorillonite Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 3
- 238000005536 corrosion prevention Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000007709 nanocrystallization Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 241000446313 Lamella Species 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 description 46
- 238000002441 X-ray diffraction Methods 0.000 description 28
- 239000010410 layer Substances 0.000 description 23
- 238000010586 diagram Methods 0.000 description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003607 modifier Substances 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 12
- 239000012528 membrane Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910021647 smectite Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 241001134446 Niveas Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241000219784 Sophora Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of tannin modified montmorillonite, which comprises the steps of dissolving a small amount of montmorillonite in more water, swelling the montmorillonite by a large amount of water to form sol and generate a Tyndall phenomenon, forming nanocrystallization by using colloidal particles which are all nano-sheets or nano-particles, and modifying the purified nanocrystallized montmorillonite by using tannin with the structural characteristic of a typical glucose galloyl compound with polyphenol hydroxyl. The method has the advantages of low raw material price, simple operation, great reduction of production cost and good modification effect; the modified montmorillonite greatly improves the compatibility problem of montmorillonite and polymer, can be widely applied to the field of corrosion prevention, can graft a group with selectivity on the surface of a lamella of the modified montmorillonite according to the anisotropic characteristic of the organic montmorillonite, can be widely applied to selectively adsorbing heavy metal ions in sewage or soil, and expands the application field of montmorillonite/polymer composite materials.
Description
(I) technical field
The invention relates to a preparation method of tannin modified montmorillonite, belonging to the technical field of montmorillonite modification.
(II) background of the invention
Montmorillonite is abundant in nature, low in price and widely exists in the surface of the earth or in the shallow region of the crust of the earth. Montmorillonite belongs to a 2. The ideal chemical formula of montmorillonite is (Na, ca) 0.33 (Al,Mg,Fe) 2 [(Si,Al) 4 O 10 ]·nH 2 And O, the structural schematic diagram of which is shown in figure 1. The montmorillonite tetrahedral layer has partial Si 4+ Is covered with Al 3+ And Fe 3+ Substitution of equivalent ions for Al in octahedron 3+ Will also be coated with Mg 2+ And Fe 2+ Substitution, which causes excess negative charge between montmorillonite layers, causes charge imbalance between crystal layers, and exhibits electronegativity, and Na is adsorbed between layers to achieve charge balance + 、K + 、Ca 2+ And Mg 2+ Etc., and thus montmorillonite has good cation exchange properties.
Montmorillonite also has the characteristics of good expansibility, adsorptivity, large specific surface area, stability, nontoxicity and the like, is applied to various fields of smelting, chemical engineering, geophysical prospecting, textile, ceramics, medicine, environmental protection, nano materials and the like at present, and practice shows that the strength, thermal stability, flame retardance, barrier property, adsorption property, mechanical property and the like of various polymers can be effectively improved by adding the montmorillonite, so that the application of the montmorillonite in the polymers gradually becomes an important application field of the montmorillonite.
Although the polymer/montmorillonite composite material has application in some fields, due to the agglomeration state and hydrophilic and oleophobic properties of montmorillonite self-packing crystals, the montmorillonite is easy to agglomerate in the polymer and difficult to effectively disperse, and is difficult to uniformly and directionally disperse in a hydrophobic polymer matrix, so that the combination of the montmorillonite and the polymer is not facilitated, the reinforcing effect of the montmorillonite on the polymer is greatly reduced, and the performance and the application range of the composite material of the montmorillonite and the polymer are limited to a certain extent. Therefore, how to prepare the montmorillonite/polymer composite membrane can increase the interlayer spacing of montmorillonite, enhance the compatibility of montmorillonite and polymer, promote the dispersibility of montmorillonite in a polymer medium, finally realize the oriented arrangement of montmorillonite in the polymer medium, and endow the montmorillonite/polymer composite membrane with anisotropic structural characteristics and characteristics is a key technical problem to be solved by inorganic and organic composite materials.
CN 108756232A discloses a method for preparing a dispersible quaternary ammonium salt modified nano organic montmorillonite, which comprises the steps of firstly using rare earth oxide to carry out chemical structure modification on montmorillonite lamellar crystals, then introducing organic quaternary ammonium salt cations in interlayer regions through ion exchange reaction to obtain the organic ammonium salt modified montmorillonite, wherein the process of carrying out chemical structure modification on the montmorillonite needs multi-step roasting procedures, the process is complex, and strong corrosive acids such as sulfuric acid, hydrochloric acid and the like need to be added. However, if the montmorillonite structure is modified to be only rare earth ions/Si-O tetrahedra or only rare earth ions/Al-O dioctahedra, the effect of being able to be sufficiently exfoliated and completely dispersed in the polymer matrix cannot be achieved.
Vanca nivea and the like (preparation of organic modified montmorillonite supported nickel catalyst and research on catalytic performance of hydrogen production by ethanol steam reforming thereof [ D ]. Taiyuan university of Taiyuan 2016) use dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide as modifiers to modify montmorillonite by a hydrothermal method, and the result shows that the interlayer spacing of montmorillonite is increased along with the increase of carbon chains and the increase of modifier dosage, but the reaction time of the modification process is longer, and the influence of physical adsorption, physical adsorption and ion exchange adsorption of basic ammonium salt needs to be considered in the modification process.
Sophora grandiflora et al (research on process of intercalation of sodium-based montmorillonite using quaternary ammonium salt [ J ]. Silicate report, 2004 (4): 98-103) firstly pretreats raw soil to obtain sodium-based montmorillonite, then adds prepared cetyl trimethyl ammonium bromide solution with certain concentration into montmorillonite suspension with certain concentration to obtain modified organic montmorillonite, and researches on influence of reaction temperature, reaction ratio, reaction time and stirring mode on intercalation effect of montmorillonite, so that the obtained montmorillonite has good modification effect under optimized conditions. However, cetyl trimethyl ammonium bromide is a single-chain quaternary ammonium salt and has no characteristics of oriented arrangement and anisotropy among molecules.
Disclosure of the invention
The invention aims to provide a preparation method of tannin modified montmorillonite, which has the advantages of low cost and simple preparation process.
The technical scheme adopted by the invention is as follows:
a method for preparing tannin modified montmorillonite, which comprises the following steps:
(1) Mixing montmorillonite and deionized water according to a mass ratio of 1; according to the experiments of dispersing the montmorillonite suspension by magnetic stirring and dispersing the montmorillonite suspension by mechanical stirring, as can be known from the data of a field emission scanning electron microscope (SEM for short), the montmorillonite dispersed by mechanical stirring in deionized water is more uniform than that dispersed by magnetic stirring, a large amount of agglomeration still exists on the surface of the montmorillonite sheet layer subjected to magnetic stirring, and the agglomeration on the surface of the montmorillonite sheet layer subjected to mechanical stirring is obviously weakened;
(2) Dissolving nano montmorillonite in deionized water under the action of mechanical stirring to prepare a nano montmorillonite suspension with the mass concentration of 0.1-2%;
(3) Dissolving tannic acid with 0.25-2.25 times of montmorillonite cation exchange capacity (0.25-2.25 CEC for short) in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution, slowly adding the tannic acid aqueous solution into the nano montmorillonite suspension under the action of mechanical stirring, and reacting in a water bath at 60-80 ℃ for 60-180 min to obtain a tannic acid modified montmorillonite suspension;
(4) After the reaction product in the step (3) is centrifugally washed for 2-5 times, 24E to 80 ℃ is dried
And grinding for 36 hours to obtain the tannin intercalation modified nano montmorillonite.
According to the invention, tannic acid is used as a modifier to modify montmorillonite, a small amount of montmorillonite is dissolved in more water, the montmorillonite is expanded by a large amount of water to form sol and generate a Tyndall phenomenon, and colloidal particles in the colloid are all nano sheets or nano particles, namely nanocrystallization is formed. Then, the purified nano-montmorillonite is modified by tannic acid with the structural characteristic of a typical glucose galloyl compound with polyphenol hydroxyl, so that the interlayer spacing of the montmorillonite is further enlarged, the enlarged interlayer spacing not only creates a space environment for inserting a high polymer, but also greatly reduces Van der Waals force between layers; secondly, montmorillonite is arranged in a polymer in an oriented way (according to a montmorillonite structure (figure 1) and a tannic acid structure (figure 2); the reaction mechanism of montmorillonite and tannic acid, and the infrared spectrum of TA-Mnt can be obtained, namely-OH on a benzene ring of tannic acid is bonded with oxygen atoms on the plane and the end of a montmorillonite sheet, and as-OH on the benzene ring of tannic acid is regularly and orderly arranged, the bonded products of the two are also regularly and orderly arranged, namely a plurality of n TA-Mnt are regularly and orderly arranged together in an oriented way), so that the polymer/montmorillonite composite film has the characteristic of anisotropy, the problem of incompatibility of montmorillonite and polymer is solved, and the method has the advantages of low cost, simple process and good modification effect.
Preferably, the montmorillonite is sodium montmorillonite and has a cation exchange capacity of 126.48mmol/100g.
Specifically, in the steps (1) and (4), the centrifugal rotating speed is 6000-8000 r/min, and the time is 5-10 min.
Specifically, the method comprises the following steps:
(1) Mixing montmorillonite and deionized water at a mass ratio of 1
Performing ultrasonic treatment for 30min, circulating for 3 times, standing for 7 days, centrifuging the middle colloid part at 8000r/min for 8min, and drying the precipitate at 70-80 deg.C for 24h to obtain nano montmorillonite;
(2) Dissolving the nano montmorillonite in deionized water under the action of mechanical stirring to prepare nano montmorillonite suspension with the mass concentration of 2%;
(3) Dissolving tannic acid with 1.75 times cation exchange amount (1.75 CEC) in deionized water under magnetic stirring to obtain tannic acid aqueous solution, slowly adding tannic acid aqueous solution into nanometer montmorillonite suspension under mechanical stirring, and reacting in 80 deg.C water bath for 180 deg.C
min, obtaining suspension of the tannin modified montmorillonite;
(4) And (4) centrifugally washing the reaction product obtained in the step (3) for 3 times, drying at 80 ℃ for 24 hours, and grinding to obtain the tannic acid intercalation modified nano montmorillonite.
The invention has the following beneficial effects:
according to the invention, the intercalation of the modifier is promoted by means of a mechanical stirring technology, and then the montmorillonite is modified by using the tannic acid with the structural characteristic of a typical glucose galloyl compound with polyphenol hydroxyl, so that the raw material is low in price, the operation is simple, the production cost is greatly reduced, and the modification effect is good; the modified montmorillonite not only has larger interlayer spacing, but also can be directionally arranged in the polymer so as to ensure that the polymer/montmorillonite composite film has the characteristic of anisotropy, greatly improve the compatibility problem of the montmorillonite and the polymer, can be widely applied to the field of corrosion prevention, can graft selective groups on the surface of a sheet layer of the montmorillonite according to the characteristic of the anisotropy of the organic montmorillonite, can be widely applied to selective adsorption of heavy metal ions in sewage or soil, and expand the application field of the montmorillonite/polymer composite material.
(IV) description of the drawings
FIG. 1 is a structural view of montmorillonite.
FIG. 2 is a structural diagram of tannic acid.
FIG. 3 is an XRD pattern of a montmorillonite raw material and a nano-sized montmorillonite.
Fig. 4 is an XRD pattern of tannic acid modified montmorillonite prepared in example 1.
FIG. 5 is a FT-IR comparison graph of tannin modified montmorillonite, montmorillonite raw material and tannin prepared in example 1.
Fig. 6 is an XRD pattern of tannic acid modified montmorillonite prepared in example 2.
FIG. 7 is a FT-IR comparison graph of tannic acid modified smectite, smectite base and tannic acid prepared according to example 2.
Fig. 8 is an XRD pattern of tannic acid modified montmorillonite prepared in example 3.
FIG. 9 is a FT-IR comparison graph of tannic acid modified montmorillonite, montmorillonite raw material and tannic acid prepared in example 3.
Fig. 10 is an XRD pattern of tannic acid modified montmorillonite prepared in example 4.
FIG. 11 is a FT-IR comparison graph of tannic acid modified smectite, smectite base and tannic acid prepared according to example 4.
Fig. 12 is an XRD pattern of tannic acid modified montmorillonite prepared in example 5.
FIG. 13 is a FT-IR comparison graph of tannic acid modified montmorillonite, montmorillonite raw material and tannic acid prepared in example 5.
Fig. 14 is an XRD pattern of tannic acid modified montmorillonite prepared in example 6.
FIG. 15 is a FT-IR comparison graph of tannic acid modified smectite, smectite base and tannic acid prepared according to example 6.
Fig. 16 is an XRD pattern of tannic acid modified montmorillonite prepared in example 7.
FIG. 17 is a FT-IR comparison graph of tannic acid modified montmorillonite, montmorillonite raw material and tannic acid prepared in example 7.
Fig. 18 is an XRD pattern of tannic acid modified montmorillonite prepared in example 8.
FIG. 19 is a FT-IR comparison graph of tannic acid modified montmorillonite, montmorillonite raw material and tannic acid prepared in example 8.
Fig. 20 is an XRD pattern of tannic acid modified montmorillonite prepared in example 9.
FIG. 21 is a FT-IR comparison graph of tannic acid modified montmorillonite, montmorillonite raw material and tannic acid prepared in example 9.
(V) detailed description of the preferred embodiments
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples:
preferentially preparing nano montmorillonite, drying for later use:
dissolving original sodium-based montmorillonite (Mnt, the cation exchange capacity is 126.48mmol/100 g) and deionized water in a mass ratio of 1.
Example 1:
dissolving 5g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 5.37g of tannic acid equivalent to 0.25 time of montmorillonite cation exchange capacity in deionized water (500 mL) under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, carrying out multiple centrifugal washing on a product after reaction, wherein the centrifugal speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structure diagram of montmorillonite is shown in figure 1, the structure diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl groups, and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer (for the reason that the details are shown in page 3), so that the polymer/montmorillonite composite membrane has anisotropic characteristics.
The XRD pattern of montmorillonite raw material is shown in FIG. 3, the XRD pattern of tannin modified montmorillonite with 0.25 times cation exchange amount of montmorillonite is shown in FIG. 4, and it can be seen that the interlayer spacing of tannin modified montmorillonite is enlarged from 1.45nm to 1.58nm, that is, the interlayer spacing is increased by 0.13nm.
The tannin modified montmorillonite and montmorillonite raw material were measured by Fourier transform infrared spectrometer (Nicolet 6700 type) of Hot Point electronic Niger, inc. in USA, and the result is shown in FIG. 5, where tannin modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 The peak of stretching vibration at C = O key disappears, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 And 1032.7cm -1 The peak intensity of characteristic peak is greatly reduced, 757.4cm -1 The bending vibration peak at O-H becomes broad. It is shown that only a small amount of tannic acid is intercalated between the montmorillonite layers to enlarge the interlayer spacing of the montmorillonite. However, the tannin has the structural characteristics of polyphenol hydroxyl, so most of phenolic hydroxyl of the tannin is complexed with sodium ions in the sodium montmorillonite.
Example 2:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 10.75g of tannic acid which is 0.50 time of montmorillonite cation exchange capacity in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of the tannic acid modified montmorillonite is shown in FIG. 6, and it can be seen that the interlayer spacing of the tannic acid modified montmorillonite is enlarged from 1.45nm to 1.58nm, namely the interlayer spacing is increased by 0.13nm, which is enlarged the same size as that of example 1.
The tannin modified montmorillonite and montmorillonite raw material were measured by Fourier transform infrared spectrometer (Nicolet 6700 type) of Hot Point electronic Niger, inc. in USA, and the result is shown in FIG. 7, where tannin modified montmorillonite (TA-Mnt) is 3625.7cm -1 And 1797.2cm -1 Stretching of montmorillonite-OHThe peak of contraction vibration and bending vibration disappeared, and tannic acid was at 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks are weakened. Similar to the infrared test results of example 1, it was demonstrated that still only a small amount of tannic acid was intercalated between the montmorillonite layers, and the interlayer spacing of the montmorillonite was enlarged.
Example 3:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 16.12g of tannic acid with the mass concentration of 0.75 time of montmorillonite cation exchange capacity in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal rotation speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of the tannic acid modified montmorillonite is shown in FIG. 8, and it can be seen that the interlayer spacing of the tannic acid modified montmorillonite is enlarged from 1.45nm to 1.52nm, namely the interlayer spacing is increased by 0.07nm, and the interlayer spacing is not enlarged much in example 2.
The results of measurement of tannin-modified montmorillonite and its raw material by Fourier transform infrared spectrometer (Nicolet 6700 type) of the Hot Point electric Niger corporation in USA are shown in FIG. 9, wherein tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and simultaneouslyTannic acid is 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks are all greatly enhanced. It is demonstrated that, in addition to a small amount of tannic acid intercalated between montmorillonite layers, since tannic acid has a structural feature of polyphenol hydroxyl group, most of phenolic hydroxyl group of tannic acid is complexed with sodium ion in sodium-based montmorillonite to displace sodium ion from montmorillonite layers, so that the interlayer distance is not much enlarged in example 2.
Example 4:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 21.50g of tannic acid with the cation exchange capacity which is 1.00 times of that of montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal rotation speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of tannin-modified montmorillonite is shown in FIG. 10, and it can be seen that the interlayer spacing of the tannin-modified montmorillonite is enlarged from 1.45nm to 1.52nm, that is, the interlayer spacing is increased by 0.07nm, which is enlarged by the same size as that of example 3.
Tannic acid modification using a Fourier transform infrared spectrometer (Nicolet 6700 type) from the US Hot Point DenigyThe results of measurements on montmorillonite and montmorillonite raw material are shown in FIG. 11, and the tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks are greatly enhanced, and are similar to the infrared test result of the example 3. It is demonstrated that, in addition to tannic acid intercalated between montmorillonite layers, since tannic acid has a structural feature of polyphenol hydroxyl group, most of phenolic hydroxyl group of tannic acid is complexed with sodium ion in sodium-based montmorillonite to displace sodium ion from montmorillonite interlayer, so that interlayer distance is not much enlarged in example 2.
Example 5:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 26.88g of tannic acid with the cation exchange capacity of 1.25 times that of montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of the tannin modified montmorillonite is shown in FIG. 12, which shows that the interlayer spacing of the tannin modified montmorillonite is enlarged from 1.45nm to 1.56nm, i.e., the interlayer spacing is increased by 0.11nm, where the interlayer spacing is enlarged more than that of example 4.
The results of measurement of tannin-modified montmorillonite and its raw material by Fourier transform infrared spectrometer (Nicolet 6700 type) of the Hot Point electric Niger corporation in USA are shown in FIG. 13, wherein tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks at (A) are all greatly enhanced. This is because tannic acid has the structural characteristics of polyphenol hydroxyl, phenolic hydroxyl of tannic acid is complexed with sodium ions in sodium-based montmorillonite, and as the addition amount of tannic acid increases, sodium ions between montmorillonite layers are completely replaced, and then hydroxyl on benzene ring of tannic acid is bonded with oxygen atoms on the plane and end of montmorillonite, which shows that tannic acid is intercalated between montmorillonite layers, and the ionic radius of tannic acid is larger than that of sodium ions, so that the interlayer distance is greatly enlarged compared with that of example 4.
Example 6:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 32.25g of tannic acid which is 1.50 times of the cation exchange capacity of the montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of the tannin modified montmorillonite is shown in FIG. 14, and it can be seen that the interlayer spacing of the tannin modified montmorillonite is enlarged from 1.45nm to 1.60nm, that is, the interlayer spacing is increased by 0.15nm, where the interlayer spacing is enlarged more than that of example 5.
The results of measurement of tannin-modified montmorillonite and its raw material by Fourier transform infrared spectrometer (Nicolet 6700 type) of the Hot Point electric Niger corporation in USA are shown in FIG. 15, wherein tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks are weakened. This is because as the amount of tannic acid added increases, hydroxyl groups on the benzene ring of tannic acid bond with more and more oxygen atoms on the montmorillonite planes and ends, indicating that tannic acid has been intercalated between the montmorillonite layers and that the ion radius of tannic acid is larger than that of sodium ions, so the interlayer spacing here is much larger than that of example 5.
Example 7:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 37.63g of tannic acid with the cation exchange capacity of 1.75 times that of montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of tannin-modified montmorillonite is shown in FIG. 16, which shows that the interlayer spacing of tannin-modified montmorillonite is enlarged from 1.45nm to 1.60nm, i.e., the interlayer spacing is increased by 0.15nm, which is enlarged by the same size as that of example 6.
The results of measurement of tannin-modified montmorillonite and its raw material by Fourier transform infrared spectrometer (Nicolet 6700 type) of the Hot Point electric Niger corporation in USA are shown in FIG. 17, wherein tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 All characteristic peaks are enhanced, similar to the infrared test result of example 6. This is because the amount of linkage of the hydroxyl group of the benzene ring of tannic acid to the oxygen atoms in the plane and terminal of montmorillonite is saturated, indicating that tannic acid has been intercalated between the montmorillonite layers, and thus the interlayer spacing is enlarged by the same size as in example 6.
Example 8:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 43.00g of tannic acid with the cation exchange capacity 2.00 times that of montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal rotation speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, and the XRD pattern of tannin modified montmorillonite is shown in FIG. 18, which shows that the interlayer spacing of tannin modified montmorillonite is enlarged from 1.45nm to 1.60nm, that is, the interlayer spacing is increased by 0.15nm, which is enlarged by the same size as in example 6.
The tannin modified montmorillonite and montmorillonite raw material were measured by Fourier transform infrared spectrometer (Nicolet 6700 type) of the American Hot Point electric Nippon corporation, and the results are shown in FIG. 19, where tannin modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 The characteristic peaks are all enhanced, and the infrared test result is similar to that of the example 6. This is because the amount of hydroxyl groups on the benzene ring of tannic acid that were bonded to the oxygen atoms on the plane and end of the smectite was saturated, indicating that tannic acid had intercalated between the smectite layers, and thus the interlayer spacing was enlarged here by the same amount as in example 6.
Example 9:
dissolving 10g of nano montmorillonite in deionized water under the action of mechanical stirring to obtain a nano montmorillonite suspension A with the mass concentration of 2%, dissolving 48.38g of tannic acid with the cation exchange capacity which is 2.25 times that of montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution B, placing the prepared suspension A and the prepared solution B in a water bath kettle at 80 ℃ under the action of magnetic stirring for mechanical stirring for 180min, centrifugally washing the product for multiple times after the reaction is finished, wherein the centrifugal rotation speed is 8000r/min, the centrifugal time is 8min each time, drying for 24h at 80 ℃, and finally grinding to obtain tannic acid modified montmorillonite (TA-Mnt).
The structural diagram of montmorillonite is shown in figure 1, the structural diagram of tannic acid is shown in figure 2, and as can be seen from figure 2, unlike the traditional single-chain quaternary ammonium salt modifier such as cetyl trimethyl ammonium bromide, tannic acid has the structural characteristics of a typical glucose galloyl compound with polyphenol hydroxyl and has a multi-chain structure, and montmorillonite organically modified by the tannic acid can be directionally arranged in a polymer, so that the polymer/montmorillonite composite membrane has the characteristic of anisotropy.
The XRD pattern of the montmorillonite raw material is shown in FIG. 3, the XRD pattern of tannin-modified montmorillonite is shown in FIG. 20, which shows that the interlayer spacing of the tannin-modified montmorillonite is enlarged from 1.45nm to 1.61nm, i.e., the interlayer spacing is increased by 0.16nm, wherein the interlayer spacing is enlarged by 0.01nm compared with that of example 8.
The results of measurement of tannin-modified montmorillonite and its raw material by Fourier transform infrared spectrometer (Nicolet 6700 type) of the Hot Point electric Niger corporation in USA are shown in FIG. 21, wherein tannin-modified montmorillonite (TA-Mnt) is 3625.7cm -1 The stretching vibration peak of montmorillonite-OH disappears, and tannin is at 1706.5cm -1 Peak of stretching vibration at C = O key, 1448.0cm -1 、1325.6cm -1 、1203.1cm -1 、1032.7cm -1 And 757.4cm -1 All characteristic peaks are enhanced, similar to the infrared test result of example 6. This is because the amount of linkage of hydroxyl groups on the benzene ring of tannic acid to oxygen atoms on the plane and end of the smectite was saturated, indicating that tannic acid had been intercalated between the smectite layers and that the interlayer spacing expanded here was only 0.01nm larger than in example 8.
From the XRD and infrared test results of the above 9 examples, when tannic acid (abbreviated as 0.25 CEC) was added in an amount of 0.25 times the cation exchange capacity of montmorillonite in this order, 0.50CEC, 0.75CEC, 1.00CEC, 1.25CEC, 1.50CEC, 1.75CEC, 2.00CEC and 2.25CEC, the interlayer spacing of the prepared tannin modified montmorillonite sample (TA-Mnt) is 1.58nm, 1.52nm, 1.56nm, 1.60nm and 1.61nm in sequence, that is, the interlayer spacing of the TA-Mnt sample was enlarged by 0.13nm, 0.07nm, 0.11nm, 0.15nm, and 0.16nm, respectively, as compared to the interlayer spacing of natural sodium-based montmorillonite of 1.45 nm. The tendency of the interlayer distance expansion shows a state of first expanding, then reducing, and then expanding.
When the amount of the tannin is 0.25CEC and 0.50CEC, only a small amount of tannin is intercalated between montmorillonite layers, so that the interlayer spacing of the montmorillonite is enlarged; when the amount of the added tannic acid is 0.75CEC and 1.00CEC, in addition to the tannic acid intercalated between the montmorillonite layers, most of phenolic hydroxyl groups of the tannic acid are complexed with sodium ions in the sodium-based montmorillonite due to the structural characteristics of polyphenol hydroxyl groups of the tannic acid, and the sodium ions are replaced from the interlayer of the montmorillonite, so that the expansion amount of the interlayer distance of the montmorillonite is reduced; when the added amount of the tannic acid is 1.25CEC and 1.50CEC, with the increase of the added amount of the tannic acid, sodium ions between montmorillonite layers are completely replaced, hydroxyl groups on benzene rings of the tannic acid are bonded with oxygen atoms on the planes and the ends of the montmorillonite, and the ionic radius of the tannic acid is larger than that of the sodium ions, so that the distance between the montmorillonite layers is enlarged; when tannic acid was added in an amount of 1.75CEC, 2.00CEC and 2.25CEC, the amount of linkage of the hydroxyl group on the benzene ring of tannic acid to the oxygen atom on the plane and the end of montmorillonite was saturated, so that the amount of expansion of the interlayer spacing of montmorillonite was not increased, and a stable state was achieved. In conclusion, 1.75CEC is the optimal addition amount of tannic acid, namely 37.63g of tannic acid.
Claims (4)
1. A method for preparing tannin modified montmorillonite, which comprises the following steps:
(1) Mixing montmorillonite and deionized water according to a mass ratio of 1;
(2) Under the action of mechanical stirring, nano montmorillonite is dissolved in deionized water to prepare nano montmorillonite suspension with the mass concentration of 0.1-2%;
(3) Dissolving tannic acid with the exchange capacity of 0.5-1.5 mol/meq montmorillonite in deionized water under the action of magnetic stirring to obtain a tannic acid aqueous solution, slowly adding the tannic acid aqueous solution into the nano montmorillonite suspension under the action of mechanical stirring, and reacting in water bath at the temperature of 60-80 ℃ for 60-180 min to obtain a tannic acid modified montmorillonite suspension;
(4) And (4) centrifugally washing the reaction product obtained in the step (3) for 2-5 times, drying at 70-80 ℃ for 24-36 hours, and grinding to obtain the tannin intercalation modified nano montmorillonite.
2. The method according to claim 1, wherein the montmorillonite is a sodium-based montmorillonite and the cation exchange capacity is 126meq/100g.
3. The method according to claim 1, wherein in steps (1) and (4), the centrifugal rotation speed is 6000 to 8000r/min and the time is 5 to 10min.
4. The method of claim 2, characterized in that the method is as follows:
(1) Mixing montmorillonite and deionized water according to a mass ratio of 1;
(2) Dissolving the nano montmorillonite in deionized water under the action of mechanical stirring to prepare nano montmorillonite suspension with the mass concentration of 2%;
(3) Dissolving tannic acid with the exchange capacity of 0.5mol/meq montmorillonite in deionized water under the action of magnetic stirring to obtain tannic acid aqueous solution, slowly adding tannic acid aqueous solution into the nano montmorillonite suspension under the action of mechanical stirring, and reacting in water bath at 80 ℃ for 180min to obtain tannic acid modified montmorillonite suspension;
(4) And (4) after centrifugal washing is carried out on the reaction product obtained in the step (3) for 3 times, drying is carried out for 24 hours at the temperature of 80 ℃, and grinding is carried out to obtain the nano montmorillonite modified by the tannic acid intercalation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280215.4A CN115744928A (en) | 2022-10-19 | 2022-10-19 | Preparation method of tannic acid modified montmorillonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211280215.4A CN115744928A (en) | 2022-10-19 | 2022-10-19 | Preparation method of tannic acid modified montmorillonite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115744928A true CN115744928A (en) | 2023-03-07 |
Family
ID=85353840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211280215.4A Pending CN115744928A (en) | 2022-10-19 | 2022-10-19 | Preparation method of tannic acid modified montmorillonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115744928A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007051427A1 (en) * | 2005-11-04 | 2007-05-10 | Zhejiang Hailisheng Pharmaceutical Limited Co. | Modified montmorillonite, method for preparing the same and use thereof |
| CN110669256A (en) * | 2019-08-29 | 2020-01-10 | 浙江工业大学 | Preparation method of hexadecylamine modified montmorillonite |
| CN110801813A (en) * | 2019-09-29 | 2020-02-18 | 浙江工业大学 | Preparation method of hexadecyl trimethyl ammonium bromide modified montmorillonite |
| CN113145072A (en) * | 2021-04-22 | 2021-07-23 | 福州大学 | Graphene/modified bentonite composite material prepared by ball milling method and application thereof |
| CN113797885A (en) * | 2021-09-07 | 2021-12-17 | 广东省科学院生态环境与土壤研究所 | Organic modified montmorillonite composite material and application thereof |
-
2022
- 2022-10-19 CN CN202211280215.4A patent/CN115744928A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007051427A1 (en) * | 2005-11-04 | 2007-05-10 | Zhejiang Hailisheng Pharmaceutical Limited Co. | Modified montmorillonite, method for preparing the same and use thereof |
| CN110669256A (en) * | 2019-08-29 | 2020-01-10 | 浙江工业大学 | Preparation method of hexadecylamine modified montmorillonite |
| CN110801813A (en) * | 2019-09-29 | 2020-02-18 | 浙江工业大学 | Preparation method of hexadecyl trimethyl ammonium bromide modified montmorillonite |
| CN113145072A (en) * | 2021-04-22 | 2021-07-23 | 福州大学 | Graphene/modified bentonite composite material prepared by ball milling method and application thereof |
| CN113797885A (en) * | 2021-09-07 | 2021-12-17 | 广东省科学院生态环境与土壤研究所 | Organic modified montmorillonite composite material and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 冯超;何光涛;李媛媛;刘文华;赵秋香;: "植物多酚改性膨润土吸附重金属镉实验研究", 环境保护科学, no. 05, pages 22 - 26 * |
| 周庶;邬杰;曹志勇;屈钧娥;王海人;: "膨润土的改性新技术及其在废水处理中的应用", 中国非金属矿工业导刊, no. 06, pages 7 - 11 * |
| 曹明礼;: "蒙脱石层间化合物的制备及应用前景", 材料导报, no. 04, 30 April 2001 (2001-04-30), pages 30 - 32 * |
| 李媛媛;刘文华;陈福强;赵秋香;: "巯基化改性膨润土对重金属的吸附性能", 环境工程学报, no. 08, 5 August 2013 (2013-08-05), pages 3013 - 3018 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gu et al. | Reagentless preparation of shape memory cellulose nanofibril aerogels decorated with Pd nanoparticles and their application in dye discoloration | |
| US5807494A (en) | Gel compositions comprising silica and functionalized carbon products | |
| CN110801813A (en) | Preparation method of hexadecyl trimethyl ammonium bromide modified montmorillonite | |
| Huang et al. | Covalent functionalization of multi-walled carbon nanotubes with quaternary ammonium groups and its application in ion chromatography | |
| CN101607298B (en) | Attapulgite suspending agent for casting alcohol-based coating and preparation method thereof | |
| CN107486135B (en) | Bentonite-coated ferroferric oxide nano material and preparation method and application thereof | |
| JP2014509667A (en) | Flexible semiconductor nanocomposite materials based on nanocrystalline cellulose and polyaniline | |
| Tran et al. | Electroconductive performance of polypyrrole/reduced graphene oxide/carbon nanotube composites synthesized via in situ oxidative polymerization | |
| Zhao et al. | Facile synthesis of phytic acid@ attapulgite nanospheres for enhanced anti-corrosion performances of coatings | |
| Ma et al. | Nanocomposites of cellulose/iron oxide: influence of synthesis conditions on their morphological behavior and thermal stability | |
| CN113831894A (en) | Ferrite graphene composite material and preparation method thereof | |
| KR101516675B1 (en) | Silica based nano sheet, dispersion sol of silica based nano sheet and method for preparing thereof | |
| Xuan et al. | Fabrication of spindle Fe2O3@ polypyrrole core/shell particles by surface-modified hematite templating and conversion to spindle polypyrrole capsules and carbon capsules | |
| Feng | Synthesis of Ag/Polypyrrole Core‐Shell Nanospheres by a Seeding Method | |
| CN108393088B (en) | Preparation method of gamma-ferric oxide/rGO composite material with flower-like microsphere structure | |
| Xiao et al. | Regulating crystallinity in cellulose substrate to construct highly and homogeneously dispersed TiO2 for tetracycline hydrochloride adsorption | |
| Kumar et al. | Synthesis and characterization of silver nanoparticle embedded cellulose–gelatin based hybrid hydrogel and its utilization in dye degradation | |
| CN115744928A (en) | Preparation method of tannic acid modified montmorillonite | |
| CN104466133B (en) | A kind of graphene carbon composite of N doping and preparation method thereof | |
| CN108439417B (en) | Preparation method of carbon nano tube coated silicon dioxide microsphere composite nano material | |
| Li et al. | Simultaneous polymerization and crosslinking for the synthesis of molecular-level graphene oxide–polyacryl amide–CeOx composites | |
| Yao et al. | Preparation and characterization of molybdenum disulfide–Sodium alginate/Antarctic krill protein composite fiber for dye adsorption | |
| CN109762221B (en) | Graphene oxide-loaded halloysite modified styrene butadiene rubber and preparation method thereof | |
| Liu et al. | Cellulose nanocrystals‐organic montmorillonite nanohybrid material by electrostatic self‐assembly | |
| Wu et al. | Controllable microemulsion method for the synthesis of Mg (OH) 2/PS core–shell structures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |