CN115672261A - Polymer-modified attapulgite containing sulfhydryl Schiff base side group and preparation method thereof - Google Patents
Polymer-modified attapulgite containing sulfhydryl Schiff base side group and preparation method thereof Download PDFInfo
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 94
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 93
- -1 sulfhydryl Schiff base Chemical class 0.000 title claims abstract description 36
- 239000002262 Schiff base Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 36
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 36
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000967 suction filtration Methods 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- VPZKJFJWKLYFQD-UHFFFAOYSA-N 3-(chloromethyl)-2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=C(CCl)C=C([N+]([O-])=O)C=C1C=O VPZKJFJWKLYFQD-UHFFFAOYSA-N 0.000 claims description 7
- YAYYVMKNPQBLRG-UHFFFAOYSA-N benzylsulfanyl(3-trimethoxysilylpropylsulfanyl)methanethione Chemical compound CO[Si](OC)(OC)CCCSC(=S)SCC1=CC=CC=C1 YAYYVMKNPQBLRG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- WPVXOOFOWPVFTK-UHFFFAOYSA-N (2-formylphenyl) nitrate Chemical compound [O-][N+](=O)OC1=CC=CC=C1C=O WPVXOOFOWPVFTK-UHFFFAOYSA-N 0.000 claims description 5
- BPYAEPMAZDQLMP-UHFFFAOYSA-N benzylsulfanyl(propylsulfanyl)methanethione Chemical compound CCCSC(=S)SCC1=CC=CC=C1 BPYAEPMAZDQLMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical group [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004753 Schiff bases Chemical group 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 3
- KFFUEVDMVNIOHA-UHFFFAOYSA-N 3-aminobenzenethiol Chemical compound NC1=CC=CC(S)=C1 KFFUEVDMVNIOHA-UHFFFAOYSA-N 0.000 claims description 3
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GDJYIXGPYCKDOV-UHFFFAOYSA-N n-phenylthiohydroxylamine Chemical compound SNC1=CC=CC=C1 GDJYIXGPYCKDOV-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 36
- 229910052753 mercury Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 238000013467 fragmentation Methods 0.000 abstract description 2
- 238000006062 fragmentation reaction Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 2
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 description 25
- 150000002500 ions Chemical class 0.000 description 24
- 239000000243 solution Substances 0.000 description 15
- 239000012467 final product Substances 0.000 description 6
- 239000005266 side chain polymer Substances 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910001987 mercury nitrate Inorganic materials 0.000 description 2
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- 206010067477 Cytogenetic abnormality Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000001727 in vivo Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000008376 long-term health Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
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- 238000007725 thermal activation Methods 0.000 description 1
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Abstract
The invention discloses attapulgite modified by polymers containing sulfhydryl Schiff base side groups and a preparation method thereof, wherein a trithioester chain transfer agent is directly modified on the surface of the attapulgite through a silane coupling agent condensation reaction, then a polymer containing polyethylene glycol monomethyl ether and tertiary amine groups on side chains is grafted on the surface of a material through a reversible addition-fragmentation chain transfer (RAFT) polymerization method, and finally the attapulgite modified by the polymers containing the sulfhydryl Schiff base side groups is prepared through a quaternization reaction and a Schiff condensation reaction; the attapulgite surface polymer modified material provided by the invention has higher adsorption capacity and stronger selective adsorption capacity on mercury ions, and can be used for adsorption, enrichment and separation of mercury ions in water.
Description
Technical Field
The invention relates to the field of high-molecular modification of inorganic clay mineral surfaces, in particular to attapulgite modified by a polymer with a side group bonded with a sulfhydryl Schiff base functional group and preparation thereof, which can be used for selective adsorption, enrichment and separation of mercury ions in water.
Background
With the development of society, pollutants in the water environment cause continuous harm to the environmental safety and human health. How to remove pollutants in wastewater efficiently is a research hotspot at present. Heavy metal ions have high toxicity to human bodies, are difficult to degrade in nature, can be absorbed and enriched in organisms through food chains, have certain concealment, and can cause serious and long-term health damage to human beings. Wherein, the mercury ions can be combined with sulfydryl in cells in vivo, seriously interfere the metabolism and functions of the cells, and cause chromosome abnormality and have teratogenesis through the action of nucleic acid and nucleotide. Therefore, the removal of mercury ions in the mercury-containing wastewater is of great significance. The heavy metal adsorbent has become a main means for removing heavy metal ions due to the advantages of convenience, rapidness, low cost and the like, and has been the research focus of people all the time.
Attapulgite, also known as palygorskite, is a water-containing magnesium-rich aluminosilicate clay mineral with chain layer structure and fiber form, is in the shape of nanorod crystals, is low in price and wide in application, and is called 'thousands of earth' and 'king of ten thousand of earth'. The attapulgite has good structural stability and large specific surface area, and meanwhile, the surface of the material contains a large number of hydroxyl functional groups, so that the material can be subjected to complexing action with heavy metal ions in a water body, and the heavy metal ions in the water body can be adsorbed and removed. The attapulgite is widely distributed in Anhui, jiangsu, shandong, liaoning and other places in China, and has large storage capacity and good grade. The attapulgite is used for treating pollution and restoring environment, can embody the characteristic of natural purification, and plays a unique role in the fields of pollution treatment and environment restoration.
However, the attapulgite needle-like rod crystals have a large specific surface area and a high surface activity, and are likely to agglomerate during use. Generally, the complexing ability of a large number of hydroxyl groups on the surface of attapulgite to heavy metal ions is not high, and the adsorption capacity and the adsorption rate of the attapulgite directly used as an adsorbent material to the heavy metal ions in a water body are relatively limited. Meanwhile, the hydroxyl groups on the surface of the attapulgite have certain effects on various heavy metal ions, and the selective adsorption and separation of specific heavy metal ions cannot be realized. In general, the adsorption treatment effect of the material on heavy metal ions can be improved by methods such as acid treatment and activation of attapulgite to remove associated impurities, thermal activation to increase the specific surface area, modification treatment with a silane coupling agent to increase surface functional groups, and the like.
Through coating or grafting the hydrophilic polymer on the surface of the attapulgite, the adsorption treatment capacity of the attapulgite on heavy metal ions can be effectively improved. The introduction of the hydrophilic polymer can obviously improve the water dispersibility of the attapulgite nano particles, and avoid agglomeration during use, which causes the reduction of the specific surface area and influences the adsorption effect. Meanwhile, a specific strong chelating group can be bonded on the polymer, so that the adsorption capacity and the selective adsorption capacity of the polymer on specific heavy metal ions are obviously improved.
Disclosure of Invention
The polymer side group grafted on the surface of the attapulgite is bonded with polyethylene glycol and a sulfhydryl Schiff base group, and the structural general formula of the attapulgite is as follows:
wherein the content of the first and second substances,refers to the nano needle-shaped rod crystal of attapulgite, R 1 ,R 2 Respectively one of hydrogen atom or methyl, x and y are the average polymerization degrees of two grafting monomers, and n is determined by the repeating unit of polyethylene glycol in the monomerAnd the terminal sulfydryl on the sulfydryl Schiff base functional group is positioned on any one of ortho-position, meta-position and para-position on a benzene ring.
The invention further provides a preparation method of the attapulgite modified by the polymer containing the sulfhydryl Schiff base side group, which comprises the following steps:
firstly, screening the attapulgite by a 200-mesh sieve to remove impurities, adding 0.15mol/L hydrochloric acid solution, mechanically stirring for 12 hours, finally washing with deionized water to be neutral, drying and grinding. Weighing pretreated attapulgite AT, dispersing the attapulgite AT in an anhydrous organic solvent, adding S-benzyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain the attapulgite AT-BTPT of the surface-modified trithiocarbonate chain transfer agent, wherein the reaction formula of the synthesis steps is expressed as follows:
step two, adding the AT-BTPT in the step one into an organic solvent, performing ultrasonic dispersion, adding a side chain polyethylene glycol monomethyl ether macromonomer, a side chain tertiary amine monomer, an azodiisobutyronitrile initiator and a small amount of S-benzyl S' -propyl trithiocarbonate BPTT as a small molecular RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to 70 ℃ and performing a light-tight reaction for 48 hours under the protection of nitrogen, allowing an open reaction bottle to contact with air for cooling to stop the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain polymer-modified attapulgite AT-P with side chains bonded with polyethylene glycol monomethyl ether and tertiary amine, wherein the reaction formula in the synthesis step is expressed as follows:
adding AT-P in the second step into acetonitrile, performing ultrasonic dispersion, slowly adding 3-chloromethyl-5-nitro salicylaldehyde 3-CS under the ice-water bath cooling condition, stirring AT room temperature for reaction for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain polymer-modified attapulgite AT-PCS with side chains bonded with polyethylene glycol monomethyl ether and nitro salicylaldehyde, wherein the reaction formula in the synthesis steps is expressed as follows:
step four, adding AT-PCS in the step three into ethanol, adding mercaptoaniline, controlling the temperature to be 50 ℃, stirring, reacting for 12 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain polymer-modified attapulgite AT-PSH with side chains bonded with polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base, wherein the reaction formula in the synthesis steps is expressed as follows:
further, the solid-liquid mass volume ratio of the attapulgite sieved and impurity removed in the first step to 0.15mol/L hydrochloric acid solution is 1; the organic solvent is selected from any one of acetone, ethanol, toluene, tetrahydrofuran and acetonitrile; the solid-liquid mass volume ratio of the AT to the organic solvent is 1; the mass of the S-benzyl S' -trimethoxysilylpropyl trithiocarbonate is 0.5 to 2 times of that of AT.
Further, the organic solvent in the second step is selected from any one of toluene, ethylbenzene, anisole, dioxane and N, N-dimethylformamide; the solid-liquid mass volume ratio of the AT to the organic solvent is 1-50 g/mL; the side chain polyethylene glycol monomethyl ether macromonomer is any one of polyethylene glycol monomethyl ether acrylate and polyethylene glycol monomethyl ether methacrylate, and the molecular weight of the side chain polyethylene glycol monomethyl ether macromonomer is 950-1000 g/moL; the side chain tertiary amine monomer is any one of dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate; the total mass of the two monomers is 5-10 times of the mass of AT-BTPT; the mass of the side chain polyethylene glycol monomethyl ether macromonomer accounts for 20-40% of the total mass of the two monomers; the mass of the azodiisobutyronitrile initiator is 1-2% of that of AT-BTPT; the mass of the small molecular RAFT reagent BPTT is 4-6 times of that of the azodiisobutyronitrile initiator.
Further, the solid-liquid mass volume ratio of AT-P to acetonitrile in the third step is 1-30 g/mL; the mass of the 3-chloromethyl-5-nitro salicylaldehyde is 0.5 to 2 times of that of AT-P.
Further, the solid-liquid mass volume ratio of AT-PCS to ethanol in the fourth step is 1-80 g/mL; the mercaptoaniline compound is selected from any one of 2-mercaptoaniline, 3-mercaptoaniline and 4-mercaptoaniline; the mass of the mercaptoaniline compound is 0.5-2 times of that of AT-PCS.
The invention has the beneficial effects that:
1. the invention modifies the surface of attapulgite with a reversible addition-fragmentation chain transfer (RAFT) reagent containing a trithioester structure. Functional polymers are introduced on the surface of the material through RAFT polymerization initiated on the surface of the material, the method is simple to operate, the grafting density on the surface of the polymer is high, the molecular weight of the grafted polymer is controllable, and the molecular weight distribution is narrow.
2. The polymer side chain grafted on the surface of the attapulgite material prepared by the invention contains polyethylene glycol and quaternary amine groups, and the groups have strong hydrophilicity, can obviously improve the water dispersibility of the adsorbing material, avoid material agglomeration and sedimentation in the water treatment process, reduce the specific surface area and reduce the adsorption capacity. The grafted hydrophilic polymer extends outwards in the water solution, which is beneficial to the rapid adsorption and removal of heavy metal ions.
3. The polymer modified attapulgite containing the sulfhydryl Schiff base side group has high adsorption capacity and selective adsorption to mercury ions through heavy metal adsorption experiments, and can be used for selective adsorption, enrichment and separation of mercury ions in water.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a Transmission Electron Microscope (TEM) image of pretreated attapulgite AT-1 and a final product AT-PSH-1 manufactured in example 1, wherein: a. TEM image of pretreated attapulgite AT-1; b. TEM image of the final product AT-PSH-1.
FIG. 2 shows the adsorption amounts of heavy metal ions by pretreated attapulgite AT-1 prepared in example 1.
FIG. 3 shows the adsorption amounts of different heavy metal ions by the attapulgite polymer-modified material AT-PSH-1 prepared in example 1.
FIG. 4 shows the adsorption amounts of two kinds of ions in a mercury-containing binary heavy metal ion mixed solution by the attapulgite polymer-modified material AT-PSH-1 prepared in example 1.
Detailed Description
To further disclose the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
firstly, screening attapulgite by a 200-mesh sieve, removing impurities, adding 0.15mol/L hydrochloric acid solution, mechanically stirring for 12 hours, wherein the solid-liquid mass volume ratio of the screened and impurity-removed attapulgite to the hydrochloric acid solution is 1. Weighing 2g of pretreated attapulgite AT-1, dispersing in 80mL of absolute ethanol, adding 2g S-benzyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain the attapulgite AT-BTPT-1 with the trithiocarbonate chain transfer agent modified on the surface.
And (II) adding 1g of AT-BTPT-1 obtained in the step one into 40mL of N, N-dimethylformamide, performing ultrasonic dispersion, adding 2g of polyethylene glycol monomethyl ether methacrylate (Mn =950 g/moL), 8g of dimethylaminoethyl methacrylate, 0.01g of azodiisobutyronitrile initiator and 0.05g S-benzyl S' -propyl trithiocarbonate as a small-molecule RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to 70 ℃, performing dark reaction for 48 hours under the protection of nitrogen, cooling and terminating the reaction by contacting air in a reaction bottle, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-1 with the surface modified polymer containing polyethylene glycol monomethyl ether and tertiary amine side chains.
And thirdly, adding 1g of AT-P-1 obtained in the second step into 20mL of acetonitrile, performing ultrasonic dispersion, slowly adding 2g of 3-chloromethyl-5-nitro salicylaldehyde under the ice-water bath cooling condition, stirring AT room temperature for reaction for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the attapulgite AT-PCS-1 with the surface modified by the side chain polymer containing the polyethylene glycol monomethyl ether and the nitro salicylaldehyde.
(IV) adding 1g of AT-PCS-1 in the third step into 50mL of ethanol, adding 2g of 2-mercaptoaniline, controlling the temperature to be 50 ℃, stirring and reacting for 12 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the attapulgite AT-PSH-1 with the surface modified polymer containing the side chain of the polyethylene glycol monomethyl ether and the mercapto salicylaldehyde Schiff base, wherein the structural formula of the final product is as follows:
example 2:
and (I) screening the attapulgite by a 200-mesh sieve to remove impurities, adding 0.15mol/L hydrochloric acid solution, mechanically stirring for 12 hours, wherein the solid-liquid mass volume ratio of the screened and impurity-removed attapulgite to the hydrochloric acid solution is 1. Weighing 2g of pretreated attapulgite AT-2, dispersing in 30mL of acetone, adding 1g S-benzyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain the attapulgite AT-BTPT-2 with the trithiocarbonate chain transfer agent modified on the surface.
And (II) adding 1g of AT-BTP-2 obtained in the step one into 30mL of toluene, performing ultrasonic dispersion, adding 1.5g of polyethylene glycol monomethyl ether acrylate (Mn =1000 g/moL), 3.5g of dimethylaminoethyl acrylate, 0.015g of azobisisobutyronitrile initiator and 0.09g S-benzyl S' -propyl trithiocarbonate as a small-molecule RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeatedly performing the operation for 3 times, controlling the temperature to be 70 ℃, performing light-resistant reaction for 48 hours under the protection of nitrogen, allowing a reaction bottle to be in open contact with air, cooling to terminate the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-2 with the surface modified by polyethylene glycol monomethyl ether and tertiary amine side chain polymers.
And (III) adding 1g of AT-P-2 obtained in the step two into 10mL of acetonitrile, performing ultrasonic dispersion, slowly adding 1g of 3-chloromethyl-5-nitro salicylaldehyde under the ice-water bath cooling condition, stirring AT room temperature for reaction for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the attapulgite AT-PCS-2 with the surface modified by the side chain polymer containing the polyethylene glycol monomethyl ether and the nitro salicylaldehyde.
(IV) adding 1g of AT-PCS-2 in the third step into 30mL of ethanol, adding 1g of 3-mercaptoaniline, controlling the temperature to be 50 ℃, stirring and reacting for 12 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the attapulgite AT-PSH-2 with the surface modified with the side chain polymer of the polyethylene glycol monomethyl ether and the mercaptosalicylaldehyde Schiff base, wherein the structural formula of the final product is as follows:
example 3:
and (I) screening the attapulgite by a 200-mesh sieve to remove impurities, adding 0.15mol/L hydrochloric acid solution, mechanically stirring for 12 hours, wherein the solid-liquid mass volume ratio of the screened and impurity-removed attapulgite to the hydrochloric acid solution is 1. Weighing 2g of pretreated attapulgite AT-3, dispersing in 50mL of acetonitrile, adding 4g S-benzyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain the attapulgite AT-BTPT-3 with the trithiocarbonate chain transfer agent modified on the surface.
And (II) adding 1g of AT-BTPT-3 obtained in the step one into 50mL of anisole, performing ultrasonic dispersion, adding 3.2g of polyethylene glycol monomethyl ether methacrylate (Mn =950 g/moL), 4.8g of dimethylaminoethyl acrylate, 0.02g of azodiisobutyronitrile initiator and 0.08g S-benzyl S' -propyl trithiocarbonate as a small-molecule RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to 70 ℃, performing dark reaction for 48 hours under the protection of nitrogen, contacting the reaction bottle with air, cooling to terminate the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-3 with the surface modified polymer containing polyethylene glycol monomethyl ether and tertiary amine side chains.
And (III) adding 1g of AT-P-3 obtained in the step II into 30mL of acetonitrile, performing ultrasonic dispersion, slowly adding 0.5g of 3-chloromethyl-5-nitro salicylaldehyde under the cooling condition of an ice water bath, stirring AT room temperature for reaction for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the attapulgite AT-PCS-3 with the surface modified by the side chain polymer containing the polyethylene glycol monomethyl ether and the nitro salicylaldehyde.
(IV) adding 1g of AT-PCS-3 in the third step into 80mL of ethanol, adding 0.5g of 4-mercaptoaniline, controlling the temperature to be 50 ℃, stirring for reaction for 12 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the attapulgite AT-PSH-3 with the surface modified with the side chain polymer of the polyethylene glycol monomethyl ether and the mercapto salicylaldehyde Schiff base, wherein the structural formula of the final product is as follows:
example 4:
firstly, the appearances of attapulgite before and after modification are observed by TEM, the attapulgite AT-1 after pretreatment is seen to be in a randomly oriented needle shape with the average diameter of about 50nm in figure 1a, and the final product AT-PSH-1 is seen to be a TEM image in figure 1b, so that a layer of polymer is obviously coated outside the needle-shaped attapulgite, and the appearance is not very regular.
Example 5:
the attapulgite AT-1 pretreated in example 1 was used as an experimental sample to study the adsorption capacity of AT-1 to different heavy metal ions.
Preparing 300mg/L aqueous solution of zinc nitrate, magnesium nitrate, chromium nitrate, cobalt nitrate, manganese sulfate and mercury nitrate, transferring the solution to a 100mL conical flask, adding pretreated attapulgite AT-1 into the solution, and setting the concentration of the attapulgite AT-1 to be 1mg/L. The pH was adjusted to 6.0 using a small amount of 20% by mass nitric acid or 30% by mass aqueous sodium acetate, respectively. Keeping the temperature at 25 ℃, oscillating the suspension at 120rpm, and centrifuging to remove the attapulgite adsorbent after 12 hours. The concentration of the heavy metal ions in the solution is detected by using an inductively coupled plasma method, the adsorption capacity is calculated, the average value is repeatedly obtained for 3 times, and the result is shown in figure 2.
The result shows that the adsorption capacity of the pretreated attapulgite AT-1 to zinc, magnesium, chromium, cobalt, manganese and mercury ions is not large, the numerical value is close to that of the attapulgite AT-1, the adsorption capacity is generally about 10mg/g, and the attapulgite AT-1 cannot show the selective adsorption performance to the mercury ions. Due to the low adsorption capacity, if the attapulgite AT-1 is directly used for removing heavy metal pollutants in a water body, the amount of the attapulgite needed in the application is large.
Example 6:
the polymer-modified attapulgite material AT-PSH-1 prepared in example 1 was used as an experimental sample to study the adsorption capacity of AT-PSH-1 to different heavy metal ions. The experimental conditions were the same as in example 5, and the results are shown in FIG. 3.
The result shows that the adsorption capacity of the polymer modified attapulgite material AT-PSH-1 to zinc, magnesium, chromium, cobalt and manganese ions is not greatly different and is about 50mg/L, however, the AT-PSH-1 has very high adsorption capacity to mercury ions and reaches 276mg/L. Therefore, the polymer modified attapulgite material AT-PSH-1 shows high affinity to mercury ions.
Example 7:
the polymer-modified attapulgite material AT-PSH-1 prepared in example 1 was used as an experimental sample to study the adsorption capacity of AT-PSH-1 to two heavy metal ions in a mercury-containing binary mixed solution. Preparing a mixed solution containing mercury binary heavy metal ions, wherein the mercury ions are from mercury nitrate, other ions are from zinc nitrate, magnesium nitrate, chromium nitrate, cobalt nitrate and manganese sulfate, the concentrations of the two metal ions in the mixed solution are respectively 300mg/L, other experimental conditions are the same as those in example 5, and the result is shown in figure 4.
The result shows that the adsorption of the polymer modified attapulgite material AT-PSH-1 to mercury ions in a binary system is much higher than that of another heavy metal ion. In a binary system, the adsorption capacity to mercury ions is more than 250mg/L, and the adsorption capacity to another heavy metal ion is in the range of 30-40 mg/L due to competitive adsorption, so that AT-PSH-1 has stronger selective adsorption to mercury ions.
Claims (6)
1. The polymer modified attapulgite containing the sulfhydryl Schiff base side group is characterized in that: the side group of the polymer grafted on the surface of the attapulgite is bonded with polyethylene glycol and sulfhydryl Schiff base groups, and the structural general formula is as follows:
wherein the content of the first and second substances,refers to the nano needle-shaped rod crystal of attapulgite, R 1 ,R 2 The two grafting monomers are respectively one of hydrogen atom or methyl, x and y are the average polymerization degrees of the two grafting monomers, n is determined by the repeating unit of polyethylene glycol on the side chain of the monomer, and the tail end sulfhydryl is positioned on any one of ortho-position, meta-position and para-position on a benzene ring.
2. The preparation method of the attapulgite modified by the polymer containing the sulfhydryl schiff base side group according to claim 1, characterized by comprising the following steps:
firstly, screening the attapulgite by a 200-mesh sieve to remove impurities, adding 0.15mol/L hydrochloric acid solution, mechanically stirring for 12 hours, finally washing with deionized water to be neutral, drying and grinding. Weighing pretreated attapulgite AT, dispersing the attapulgite AT in an organic solvent, adding S-benzyl S' -trimethoxysilylpropyl trithiocarbonate, refluxing for 12 hours under the protection of nitrogen, cooling, performing suction filtration, washing with ethanol, and performing vacuum drying to obtain the attapulgite AT-BTPT of the trithiocarbonate chain transfer agent for surface modification, wherein the reaction formula of the synthesis steps is expressed as follows:
step two, adding the AT-BTPT in the step one into an organic solvent, performing ultrasonic dispersion, adding a side chain polyethylene glycol monomethyl ether macromonomer, a side chain tertiary amine monomer, an azodiisobutyronitrile initiator and a small amount of S-benzyl S' -propyl trithiocarbonate BPTT as a small molecular RAFT reagent to improve the polymerization controllability, vacuumizing, introducing high-purity nitrogen, repeating the operation for 3 times, controlling the temperature to 70 ℃ and performing a light-tight reaction for 48 hours under the protection of nitrogen, allowing an open reaction bottle to contact with air for cooling to stop the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain polymer-modified attapulgite AT-P with side chains bonded with polyethylene glycol monomethyl ether and tertiary amine, wherein the reaction formula in the synthesis step is expressed as follows:
adding AT-P in the second step into acetonitrile, performing ultrasonic dispersion, slowly adding 3-chloromethyl-5-nitro salicylaldehyde 3-CS under the ice-water bath cooling condition, stirring AT room temperature for reaction for 24 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain polymer-modified attapulgite AT-PCS with side chains bonded with polyethylene glycol monomethyl ether and nitro salicylaldehyde, wherein the reaction formula in the synthesis steps is expressed as follows:
step four, adding AT-PCS in the step three into ethanol, adding mercaptoaniline, controlling the temperature to be 50 ℃, stirring, reacting for 12 hours, then performing suction filtration, washing with acetone, and performing vacuum drying to obtain polymer-modified attapulgite AT-PSH with side chains bonded with polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base, wherein the reaction formula in the synthesis steps is expressed as follows:
3. the method for preparing the attapulgite modified by the polymer containing the sulfhydryl schiff base side group according to claim 2, wherein the method comprises the following steps: the solid-liquid mass-volume ratio of the attapulgite sieved and impurity-removed in the first step to 0.15mol/L hydrochloric acid solution is 1; the organic solvent is selected from any one of acetone, ethanol, toluene, tetrahydrofuran and acetonitrile; the solid-liquid mass volume ratio of the AT to the organic solvent is 1; the mass of the S-benzyl S' -trimethoxysilylpropyl trithiocarbonate is 0.5 to 2 times of that of AT.
4. The method for preparing the attapulgite modified by the polymer containing the sulfhydryl schiff base side group according to claim 2, wherein the method comprises the following steps: the organic solvent in the second step is selected from any one of toluene, ethylbenzene, anisole, dioxane and N, N-dimethylformamide; the solid-liquid mass volume ratio of the AT to the organic solvent is 1-50 g/mL; the side chain polyethylene glycol monomethyl ether macromonomer is any one of polyethylene glycol monomethyl ether acrylate and polyethylene glycol monomethyl ether methacrylate, and the molecular weight of the side chain polyethylene glycol monomethyl ether macromonomer is 950-1000 g/moL; the side chain tertiary amine monomer is any one of dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate; the total mass of the two monomers is 5-10 times of the mass of AT-BTPT; the mass of the side chain polyethylene glycol monomethyl ether macromonomer accounts for 20-40% of the total mass of the two monomers; the mass of the azodiisobutyronitrile initiator is 1-2% of that of AT-BTPT; the mass of the small molecular RAFT reagent BPTT is 4-6 times of that of the azodiisobutyronitrile initiator.
5. The method for preparing the attapulgite modified by the polymer containing the sulfhydryl schiff base side group according to claim 2, wherein the method comprises the following steps: the solid-liquid mass volume ratio of AT-P to acetonitrile in the third step is 1-30 g/mL; the mass of the 3-chloromethyl-5-nitro salicylaldehyde is 0.5 to 2 times of that of the AT-P.
6. The method for preparing the attapulgite modified by the polymer containing the sulfhydryl schiff base side group according to claim 2, wherein the method comprises the following steps: the solid-liquid mass-volume ratio of AT-PCS to ethanol in the fourth step is 1-80 g/mL; the mercaptoaniline compound is selected from any one of 2-mercaptoaniline, 3-mercaptoaniline and 4-mercaptoaniline; the mass of the mercaptoaniline compound is 0.5-2 times of that of AT-PCS.
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