CN102114412A - Chitosan-grafted and modified attapulgite clay absorbing material and preparation method thereof - Google Patents
Chitosan-grafted and modified attapulgite clay absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a chitosan-grafted and modified attapulgite clay absorbing material and a preparation method thereof, belonging to the technical field of new materials. The chitosan-grafted and modified attapulgite clay absorbing material is prepared by using chitosan and organic attapulgite clay as raw materials through dialdehyde crosslinking. The preparation method comprises the steps of: modifying the attapulgite clay by adopting an aminosilane coupling agent to prepare the organic attapulgite clay; then, dispersing the organic attapulgite clay into a dialdehyde solution, stirring at a temperature of 30 DEG C for 3-4h to prepare the dialdehyde modified attapulgite clay; then dropping a chitosan solution in a dialdehyde-modified attapulgite clay suspension, reacting at a temperature of 30-45 DEG C for 3-5h, reducing with a reducing agent at room temperature under the alkalinity condition, fully washing with deionized water, drying in vacuum, grinding and screening to obtain the chitosan-grafted and modified attapulgite clay. The chitosan is bonded on the surface of the attapulgite clay in a covalent bond manner, thus the bonding firmness of the chitosan and the attapulgite clay is greatly improved. The chitosan-grafted and modified attapulgite clay prepared with the method provided by the invention has better absorbing property to various dyes.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of organic surface modifying method of attapulgite, be specially the preparation method of the attapulgite modified sorbing material of a kind of chitosan graft.
Background technology
Attapulgite is that a kind of porous type chain stratiform contains Shuifu County's zeopan class clay mineral, and its theoretical chemistry formula is Si
8Mg
5O
20(OH)
2(H
2O)
44H
2O, the skeleton structure of attapulgite is the 3 D stereo shape, interconnect by shared summit by silicon-oxy tetrahedron and magnalium octahedron and to form, zeolite cavity and hole run through total, be a kind of porous mineral matter, crystal structure inside has a large amount of zeolite channels, and crystals zeolite cavity size unanimity, make its effect, can be used for the absorption of various industrial wastewaters with molecular sieve.For improving the absorption property of attapulgite, need carry out suitable modification to it usually and handle.Method of modifying commonly used mainly contains: acid activation modification, high-temperature roasting modification and organically-modified.Acid activation modification and high-temperature roasting modification mainly are that partial impurities makes the open and enlarged-diameter in attapulgite duct in the attapulgite by removing, and specific area increases, and absorption property strengthens.The organically-modified electronegative characteristic of attapulgite's surface of mainly utilizing, adopt cationic surfactant to its modification, as: the attapulgite modified absorption (publication number: CN1793242A, a kind of preparation method of attapulgite of cationic surfactant modification) that is used for phenol of employing cationic surfactants such as Wang Xingguo; Employing long-chain alkylguanidine-modified attapulgites such as Chen Tiantian are used for the absorption (publication number: CN101538047A, the preparation method of long-chain alkylguanidine-modified attapulgite) of waste water from dyestuff.
Shitosan is chitin hydrolysis and slough the derivative that generates behind the part acetyl group under alkali condition, a large amount of free-NH that contains in the molecule
2,-OH can borrow hydrogen bond, ionic bond to form and have similar cancellated cage type molecule, and metal ion, dye molecule are had good adsorption property.
Adopt attapulgite and shitosan can give full play to both advantages, simultaneously, can improve significantly that shitosan sorbing material settling property in solution is poor, separation difficulty, the defective that in acid solution, easily runs off for the feedstock production composite adsorbing material.The mode that people such as Li Zengxin, Yin Jingzhou once adopted dipping on attapulgite, is made solid compound adsorbent with chitosan loaded, is used for absorption (the attapulgite load shitosan absorption waste water Cd of heavy metal ions in wastewater
2+Research, nonmetallic ore, 2008 the 4th phases; Chitin modified attapulgite is to the absorption of heavy metal ion, chemical industry environmental protection, 2007 the 3rd phases).
Said method mainly is to cationic interchangeability according to attapulgite, utilize shitosan in acid solution, to have the characteristic of positive charge, with chitosan loaded on attapulgite, the combination of shitosan and attapulgite is the physical absorption of shitosan in attapulgite's surface, both are not in conjunction with firm, and the performance of material is not high.
Summary of the invention:
For overcoming the deficiencies in the prior art, the invention provides the preparation method of the attapulgite modified sorbing material of a kind of chitosan graft, this method is utilized the reactivity of active amino in attapulgite's surface silicon hydroxyl and the chitosan molecule, mode by chemical bonding with chitosan graft to attapulgite, can significantly improve shitosan attapulgite's surface in conjunction with fastness, give full play to both absorption properties.
The technical scheme that realizes above-mentioned purpose is: the attapulgite modified sorbing material of chitosan graft is a raw material with shitosan, organic attapulgite soil, makes by dialdehyde is crosslinked; Its molecular weight of wherein used shitosan is 1.1-2.5 * 10
5, deacetylation is 75-95%; Used organic attapulgite soil is that dialdehyde is attapulgite modified; Wherein the attapulgite modified mass ratio of shitosan and dialdehyde is: 1:1-1:2, used dialdehyde are glyoxal or glutaraldehyde.
The preparation method of the attapulgite modified sorbing material of chitosan graft provided by the invention, carry out according to following step:
(1) the attapulgite powder is scattered in the organic solvent with solid-liquid mass ratio 1:10-1:30, ultrasonic dispersion 10-30min drips amino silicane coupling agent, 70-100 ℃ of reaction 6-10h; After reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets silane coupler modified organic attapulgite soil;
(2) above-mentioned silane coupler modified organic attapulgite soil being scattered in is in the 5% dialdehyde solution in mass, and the solid-liquid mass ratio is 1:10-1:25, and 30 ℃ are stirred 3-4h, filter, deionized water repeatedly washs, vacuum drying, and it is attapulgite modified promptly to get dialdehyde;
(3) shitosan being dissolved in quality counts and is made into quality in 1% acetum and volume ratio is the chitosan-acetic acid solution of 0.5%-1.5%, stir 3h, being added drop-wise to quality and volume ratio is in the attapulgite modified suspension of 1-2% dialdehyde, stirring also is heated to 30-45 ℃, reaction 3-5h, centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, add reducing agent room temperature reduction 10-12h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
Wherein the used organic solvent of step (1) is toluene or dimethylbenzene.
Wherein the used amino silicane coupling agent of step (1) is: a kind of in gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, γ-aminopropyl methyldiethoxysilane, the γ-aminopropyl methyl dimethoxysilane, wherein the mass ratio of amino silicane coupling agent and attapulgite is 1:1.
Wherein the used dialdehyde of step (2) is glyoxal or glutaraldehyde.
Wherein the used reducing agent of step (3) is sodium borohydride or sodium cyanoborohydride, the concentration 3mol/L of reducing agent; The attapulgite modified mass ratio of shitosan and dialdehyde is 1:1-1:2.
Wherein used its molecular weight of shitosan of step (3) is 1.1-2.5 * 10
5, deacetylation is 75-95%.
As shown from the above technical solution: the present invention at first introduces amino by amino silicane coupling agent in inorganic attapulgite's surface; Then, adopt dialdehyde as crosslinking agent, amino on the chitosan molecule and attapulgite modified surface amino groups is crosslinked, thus the covalent bond of realization shitosan and attapulgite.
The attapulgite modified sorbing material advantage of chitosan graft of the present invention is:
(1) adopt natural high polymer that attapulgite is carried out graft modification, environmental protection.
(2) mode by covalent bond arrives attapulgite's surface with chitosan graft, and both adhesions are strong, and sorbing material separates in solution easily.
(3) chitosan graft is attapulgite modified all has good adsorption property to various dyestuffs.
The specific embodiment
Employed term among the present invention unless other explanation is arranged, generally has the implication of those of ordinary skills' common sense.
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
The 10g attapulgite is scattered in the 100mL toluene, ultrasonic dispersion 30min under the stirring condition, drips the 10g gamma-aminopropyl-triethoxy-silane, after dripping, be heated to 70 ℃, reaction 10h is after reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets silane coupler modified organic attapulgite soil.
It is in 5% glutaraldehyde solution in mass that gained organic attapulgite soil is dispersed in 150mL, behind 30 ℃ of reaction 3h, filter, and after deionized water repeatedly washs, vacuum drying, it is attapulgite modified promptly to get aldehyde radical.
The 1g shitosan is dissolved in quality counts that to be made into quality and volume ratio in 1% acetum be 0.5% chitosan-acetic acid solution, stir 3h, being added drop-wise to 100mL quality and volume ratio is in the 1% aldehyde radical attapulgite suspension, stirring also is heated to 30 ℃, behind the reaction 5h, and centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, use 3mol/LNaBH
4Solution room temperature reduction 12h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
Embodiment 2
The 10g attapulgite is scattered in the 300mL dimethylbenzene, ultrasonic dispersion 10min under the stirring condition, drips 10g γ-aminopropyl methyl dimethoxysilane, after dripping, be heated to 100 ℃, behind the reaction 6h, after reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets attapulgite modified by silane coupling agent.
It is in 5% glyoxal solution in mass that gained organic attapulgite soil is dispersed in 250mL, behind 30 ℃ of reaction 4h, filter, and after deionized water repeatedly washs, vacuum drying, it is attapulgite modified promptly to get aldehyde radical.
The 1g shitosan is dissolved in quality counts that to be made into quality and volume ratio in 1% acetum be 1.5% chitosan-acetic acid solution, stir 3h, being added drop-wise to 100mL quality and volume ratio is in the 2% aldehyde radical attapulgite suspension, stirring also is heated to 45 ℃, behind the reaction 3h, and centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, use 3mol/LNaBH
4Solution room temperature reduction 10h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
Embodiment 3
The 10g attapulgite is scattered in the 200mL toluene, and ultrasonic dispersion 20min under the stirring condition, drips the 10g γ-An Bingjisanjiayangjiguiwan, after dripping, be heated to 80 ℃, behind the reaction 8h, after reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets attapulgite modified by silane coupling agent.
It is in 5% glutaraldehyde solution in mass that the gained attapulgite modified by silane coupling agent is dispersed in 100mL, behind 30 ℃ of reaction 4h, filter, and after deionized water repeatedly washs, vacuum drying, it is attapulgite modified promptly to get aldehyde radical.
The 1g shitosan is dissolved in quality counts that to be made into quality and volume ratio in 1% acetum be 1% chitosan-acetic acid solution, stir 3h, being added drop-wise to 100mL quality and volume ratio is in the 1.5% aldehyde radical attapulgite suspension, stirring also is heated to 40 ℃, behind the reaction 4h, and centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, use 3mol/LNaBH
3(CN) solution room temperature reduction 10h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
Embodiment 4
The 10g attapulgite is scattered in the 250mL dimethylbenzene, ultrasonic dispersion 20min under the stirring condition, drips 10gN-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, after dripping, be heated to 90 ℃, behind the reaction 7h, after reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets attapulgite modified by silane coupling agent.
It is in 5% glyoxal solution in mass that the gained attapulgite modified by silane coupling agent is dispersed in 200mL, behind 30 ℃ of reaction 3h, filter, and after deionized water repeatedly washs, vacuum drying, it is attapulgite modified promptly to get aldehyde radical.
The 1g shitosan is dissolved in quality counts that to be made into quality and volume ratio in 1% acetum be 1% chitosan-acetic acid solution, stir 3h, being added drop-wise to 100mL quality and volume ratio is in the 1% aldehyde radical attapulgite suspension, stirring also is heated to 35 ℃, behind the reaction 4h, and centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, use 3mol/LNaBH
3(CN) solution room temperature reduction 12h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
Test one
Dyestuff adsorption experiment: select for use active yellow 3 R S, reactive red 3BS, weak acid brilliant blue 2R, acid green B, C.I. disperse yellow 54, C.I. disperse red 60, C.I. Disperse Blue-56 to be mixed with 500 mgL respectively
-1Dye wastewater.Measure dye wastewater sample 50 mL in conical flask, add 0.2 g attapulgite (attapulgite wherein comprises the attapulgite modified and concavo-convex excellent original soil of chitosan graft) respectively, be placed into vibration 180 min in 25 ℃ of constant temperature oscillators, centrifugation then, get supernatant liquor, in the maximum absorption wave strong point, the concentration of dyestuff when the initial sum of measuring each water sample reaches balance is calculated as follows the adsorbance of dyestuff with spectrophotometer.
Adsorbance
In the formula: C
0Original concentration (the mgL of-dye solution
-1); C
eEquilibrium concentration (the mgL of-dye solution
-1); The volume of V-dye solution (L); The dosage (g) that m-chitosan graft is attapulgite modified.
Embodiment 1,2,3,4 products therefroms and concavo-convex excellent original soil are carried out various dyestuff adsorption experiments, and the result is as follows:
The attapulgite modified absorption property of table 1 to various dyestuffs
Can find out from the experimental result of last table, compare with concavo-convex excellent original soil, attapulgite modified to reactive dye (active yellow 3 R S, reactive red 3BS), acid dyes (weak acid brilliant blue 2R, acid green B), disperse dyes (C.I. disperse yellow 54, C.I. absorption property Disperse Blue-56, C.I. disperse red 60) significantly improves.
Claims (7)
1. the attapulgite modified sorbing material of chitosan graft is characterized in that with shitosan, organic attapulgite soil be raw material, makes by dialdehyde is crosslinked; Its molecular weight of wherein used shitosan is 1.1-2.5 * 10
5, deacetylation is 75-95%; Used organic attapulgite soil is that dialdehyde is attapulgite modified; Wherein the attapulgite modified mass ratio of shitosan and dialdehyde is: 1:1-1:2, used dialdehyde are glyoxal or glutaraldehyde.
2. the preparation method of the attapulgite modified sorbing material of chitosan graft, it is characterized in that carrying out according to following step: (1) is scattered in the attapulgite powder in the organic solvent with solid-liquid mass ratio 1:10-1:30, ultrasonic dispersion 10-30min, drip amino silicane coupling agent, 70-100 ℃ of reaction 6-10h; After reaction finishes, remove and desolvate, vacuum drying, grinding is sieved, and promptly gets silane coupler modified organic attapulgite soil; (2) above-mentioned silane coupler modified organic attapulgite soil being scattered in is in the 5% dialdehyde solution in mass, and the solid-liquid mass ratio is 1:10-1:25, and 30 ℃ are stirred 3-4h, filter, and deionized water repeatedly washs, vacuum drying, and it is attapulgite modified promptly to get dialdehyde; (3) shitosan being dissolved in quality counts and is made into quality in 1% acetum and volume ratio is the chitosan-acetic acid solution of 0.5%-1.5%, stir 3h, being added drop-wise to quality and volume ratio is in the attapulgite modified suspension of 1-2% dialdehyde, stirring also is heated to 30-45 ℃, reaction 3-5h, centrifugation, fully washing, remove the not shitosan of covalent cross-linking, under alkali condition, add reducing agent room temperature reduction 10-12h, after deionized water fully washs, vacuum drying, grinding is sieved, and it is attapulgite modified promptly to get chitosan graft.
3. the preparation method of the attapulgite modified sorbing material of chitosan graft according to claim 2 is characterized in that wherein the used organic solvent of step (1) is toluene or dimethylbenzene.
4. the preparation method of the attapulgite modified sorbing material of chitosan graft according to claim 2, it is characterized in that wherein the used amino silicane coupling agent of step (1) is: gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, γ-aminopropyl methyldiethoxysilane, a kind of in γ-aminopropyl methyl dimethoxysilane, wherein the mass ratio of amino silicane coupling agent and attapulgite is 1:1.
5. the preparation method of the attapulgite modified sorbing material of chitosan graft according to claim 2 is characterized in that wherein the used dialdehyde of step (2) is glyoxal or glutaraldehyde.
6. the preparation method of the attapulgite modified sorbing material of chitosan graft according to claim 2 is characterized in that wherein the used reducing agent of step (3) is sodium borohydride or sodium cyanoborohydride, the concentration 3mol/L of reducing agent; The attapulgite modified mass ratio of shitosan and dialdehyde is 1:1-1:2.
7. the preparation method of the attapulgite modified sorbing material of chitosan graft according to claim 2 is characterized in that wherein used its molecular weight of shitosan of step (3) is 1.1-2.5 * 10
5, deacetylation is 75-95%.
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Effective date of registration: 20151028 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |