CN115672261B - Sulfhydryl Schiff base side group-containing polymer modified attapulgite and preparation method thereof - Google Patents
Sulfhydryl Schiff base side group-containing polymer modified attapulgite and preparation method thereof Download PDFInfo
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 91
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- -1 Sulfhydryl Schiff base Chemical class 0.000 title claims abstract description 28
- 239000002262 Schiff base Substances 0.000 title claims abstract description 9
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 43
- 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 24
- 238000005406 washing Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 15
- 238000001291 vacuum drying 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 13
- 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 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 10
- 238000003756 stirring Methods 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
- 239000000203 mixture Substances 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 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
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical group [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 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
- 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
- 238000010992 reflux Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000006757 chemical reactions by type 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- OETRDPZIXKVAQS-UHFFFAOYSA-N propylsulfanylmethanedithioic acid Chemical compound CCCSC(S)=S OETRDPZIXKVAQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 35
- 229910052753 mercury Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 6
- 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 14
- 235000019441 ethanol Nutrition 0.000 description 10
- 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
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 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
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 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
- 239000012989 trithiocarbonate Substances 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
- 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
- 230000006378 damage Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 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
- 238000010907 mechanical stirring Methods 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 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
- 238000010306 acid treatment Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 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
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 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
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 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
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polymer modified attapulgite containing sulfhydryl Schiff base side group 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 is grafted on the surface of a material through a reversible addition-fragmentation chain transfer (RAFT) polymerization method, and finally the polymer modified attapulgite containing sulfhydryl Schiff base side group 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 for 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 polymer modification on the surface of inorganic clay minerals, in particular to attapulgite modified by a polymer with a side group bonded with a sulfhydryl Schiff base functional group and a preparation method 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 environmental safety and human health. How to efficiently remove pollutants in wastewater is a research hotspot today. Heavy metal ions have higher 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, mercury ions can be combined with sulfhydryl groups in cells in vivo to seriously interfere with metabolism and functions of the cells, and simultaneously cause chromosome abnormality and have teratogenic effect through the actions of nucleic acid and nucleotide. Therefore, the removal of mercury ions in mercury-containing wastewater is of great significance. Heavy metal adsorbents have become the main means for removing heavy metal ions due to the advantages of convenience, rapidness, low cost and the like, and have been the focus of research for people.
Attapulgite, also called palygorskite, is a water-containing magnesium-rich aluminosilicate clay mineral with a chain layered structure and a fiber form, has a nano rod crystal morphology, is low in cost and wide in application, and is called as 'thousands of clay' and 'thousands of clay' in use. 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, and can be subjected to complexation with heavy metal ions in a water body, so that the heavy metal ions in the water body are adsorbed and removed. The attapulgite is widely distributed in the places such as Anhui, jiangsu, shandong, liaoning and the like in China, and has large reserves and excellent grade. The attapulgite is utilized to treat pollution and restore environment, can embody the characteristic of natural purification, and plays a unique role in the field of pollution treatment and environment restoration.
However, the attapulgite needle-like rod crystals have large specific surface area and high surface activity, so that agglomeration is easy to occur in the use process. In general, the complexing capacity of a large number of hydroxyl groups existing on the surface of the attapulgite for heavy metal ions is not high, and the adsorption capacity and adsorption rate of the attapulgite directly used as an adsorbent material for heavy metal ions in water are limited. Meanwhile, the hydroxyl groups on the surface of the attapulgite have a certain effect on various heavy metal ions, and the selective adsorption and separation of specific heavy metal ions cannot be realized. In general, the method of acid treatment, activation and removal of associated impurities, thermal activation of the attapulgite to increase the specific surface area, modification treatment of the silane coupling agent to increase the surface functional groups and the like can be adopted to improve the adsorption treatment effect of the material on heavy metal ions.
The adsorption treatment capacity of the attapulgite on heavy metal ions can be effectively improved by coating or grafting hydrophilic polymers on the surface of the attapulgite. The hydrophilic polymer can obviously improve the water dispersibility of the attapulgite nano particles, avoid agglomeration during use, reduce the specific surface area and influence the adsorption effect. Meanwhile, specific strong chelating groups can be bonded on the polymer, so that the adsorption capacity and selective adsorption capacity for specific heavy metal ions are remarkably 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 is as follows:
wherein,refers to nano needle-like rod crystal of attapulgite, R 1 ，R 2 And the monomer is one of hydrogen atoms or methyl groups, x and y are average polymerization degrees of two grafting monomers, n is determined by a repeating unit of polyethylene glycol in the monomers, and terminal mercapto on a mercapto Schiff base functional group is positioned at 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:
step one, the attapulgite is filtered by a 200-mesh sieve to remove impurities, then 0.15mol/L hydrochloric acid solution is added to be mechanically stirred for 12 hours, finally deionized water is used for washing to be neutral, and the mixture is dried and ground. The pretreated attapulgite AT is weighed and dispersed in an anhydrous organic solvent, S-benzyl S' -trimethoxy silicone propyl trithiocarbonate is added, reflux is carried out for 12 hours under the protection of nitrogen, cooling and suction filtration are carried out, ethanol is used for washing, vacuum drying is carried out, and the attapulgite AT-BTPT of the surface modified trithiocarbonate chain transfer agent is obtained, wherein the reaction formula of the synthesis steps is as follows:
adding the AT-BTPT in the first step into an organic solvent, performing ultrasonic dispersion, adding a side chain polyethylene glycol monomethyl ether macromonomer, a side chain tertiary amine monomer, an azo diisobutyronitrile initiator and a small amount of S-benzyl S' -propyl trithiocarbonate BPTT as a small molecule RAFT reagent to improve the controllability of polymerization, vacuumizing, introducing high-purity nitrogen, repeatedly performing operation for 3 times, controlling the temperature to be 70 ℃ and performing light-proof reaction for 48 hours under the protection of the nitrogen, enabling a reaction bottle to be exposed to air, cooling, stopping the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the polymer modified attapulgite AT-P with the side chain bonded polyethylene glycol monomethyl ether and tertiary amine, wherein the reaction formula of the above synthesis steps is expressed as follows:
step three, firstly adding the AT-P in the step two into acetonitrile, carrying out ultrasonic dispersion, slowly adding 3-chloromethyl-5-nitrosalicylaldehyde 3-CS under the cooling condition of ice water bath, stirring AT room temperature for reaction for 24 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the polymer modified attapulgite AT-PCS with the side chains bonded with polyethylene glycol monomethyl ether and nitrosalicylaldehyde, wherein the reaction type of the synthesis steps is as follows:
adding the AT-PCS in the step three into ethanol, adding mercaptoaniline, stirring AT the temperature of 50 ℃ for reacting for 12 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the polymer modified attapulgite AT-PSH with the side chains bonded with polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base, wherein the reaction formula of the synthesis steps is as follows:
further, the solid-liquid mass volume ratio of the attapulgite subjected to sieving and impurity removal in the first step to the hydrochloric acid solution of 0.15mol/L is 1:15-30 g/mL; 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 1:15-40 g/mL; the mass of the S-benzyl S' -trimethoxysilylpropyl trithiocarbonate is 0.5-2 times of the mass of the 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 1:30-50 g/mL; the side chain polyethylene glycol monomethyl ether macromer 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 macromer 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 the 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 the mass of the AT-BTPT; the mass of the small molecule RAFT reagent BPTT is 4-6 times of that of the azo-bis-isobutyronitrile initiator.
Further, the solid-liquid mass volume ratio of AT-P to acetonitrile in the step three is 1:10-30 g/mL; the mass of the 3-chloromethyl-5-nitro salicylaldehyde is 0.5-2 times of that of AT-P.
Further, the solid-liquid mass volume ratio of the AT-PCS to the ethanol in the fourth step is 1:30-80 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 the mass of the AT-PCS.
The beneficial effects of the invention are as follows:
1. the invention modifies the reversible addition-fragmentation chain transfer (RAFT) reagent containing trithio ester structure on the surface of the attapulgite. Functional polymer is 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 of the polymer surface is high, the molecular weight of the grafted polymer is controllable, and the molecular weight distribution is narrower.
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, so that the water dispersibility of the adsorption material can be obviously improved, the agglomeration and sedimentation of the material in the water treatment process are avoided, the specific surface area is reduced, and the adsorption capacity is reduced. The grafted hydrophilic polymer stretches outwards in the aqueous solution, which is favorable for rapid adsorption removal of heavy metal ions.
3. The sulfhydryl Schiff base group has strong binding capacity to mercury ions, and the attapulgite modified by the sulfhydryl Schiff base side group-containing polymer has higher adsorption capacity and selective adsorptivity to mercury ions through the test of heavy metal adsorption experiments, and can be used for selective adsorption and enrichment 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 that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a Transmission Electron Microscope (TEM) image of the pretreated attapulgite AT-1 prepared in example 1 and the final product AT-PSH-1, wherein: a. a TEM image of the pretreated attapulgite AT-1; b. TEM image of the final product AT-PSH-1.
FIG. 2 shows the adsorption amounts of different heavy metal ions by the pretreated attapulgite AT-1 prepared in example 1.
FIG. 3 shows the adsorption amounts of various heavy metal ions by the polymer modified attapulgite polymer materials AT-PSH-1 prepared in example 1.
FIG. 4 shows the adsorption amounts of two ions in the mixed solution of mercury-containing binary heavy metal ions by the attapulgite polymer modification material AT-PSH-1 prepared in example 1.
Detailed Description
In order to further disclose the technical solutions of the present invention, the technical solutions of 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 apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1:
the attapulgite is filtered by a 200-mesh sieve to remove impurities, then 0.15mol/L hydrochloric acid solution is added for mechanical stirring for 12 hours, wherein the solid-liquid mass volume ratio of the attapulgite after the sieving and the impurity removal to the hydrochloric acid solution is 1:20g/mL, finally deionized water is used for washing to be neutral, and the mixture is dried and ground. 2g of pretreated attapulgite AT-1 is weighed, dispersed in 80mL of absolute ethyl alcohol, 2g S-benzyl S' -trimethoxy silicon propyl trithiocarbonate is added, reflux is carried out for 12 hours under the protection of nitrogen, cooling and suction filtration are carried out, ethanol is used for washing, and vacuum drying is carried out, thus obtaining the attapulgite AT-BTPT-1 with the surface modified trithiocarbonate chain transfer agent.
And (II) adding 1g of AT-BTPT-1 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 small molecule RAFT reagent to improve the controllability of polymerization, vacuumizing, introducing high-purity nitrogen, repeatedly operating for 3 times, controlling the temperature to be 70 ℃ for light-proof reaction for 48 hours under the protection of nitrogen, performing air cooling on an opened reaction bottle, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-1 with the surface modified with polyethylene glycol monomethyl ether and tertiary amine side chain polymer.
And thirdly, firstly adding 1g of AT-P-1 in the second step into 20mL of acetonitrile, performing ultrasonic dispersion, slowly adding 2g of 3-chloromethyl-5-nitrosalicylaldehyde 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-1 with the surface modified with polyethylene glycol monomethyl ether and nitrosalicylaldehyde side chain polymers.
Adding 1g of AT-PCS-1 in the step three into 50mL of ethanol, adding 2g of 2-mercaptoaniline, stirring AT the temperature of 50 ℃ for reaction for 12 hours, filtering, washing with acetone, and drying in vacuum to obtain the attapulgite AT-PSH-1 with the surface modified with the polymer containing polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base side chains, wherein the structural formula of the final product is as follows:
example 2:
the attapulgite is filtered by a 200-mesh sieve to remove impurities, then 0.15mol/L hydrochloric acid solution is added to be mechanically stirred for 12 hours, wherein the solid-liquid mass volume ratio of the attapulgite after the sieving and the impurity removal to the hydrochloric acid solution is 1:15g/mL, finally deionized water is used for washing to be neutral, and the mixture is dried and ground. 2g of pretreated attapulgite AT-2 is weighed, dispersed in 30mL of acetone, and 1g S-benzyl S' -trimethoxy silicon propyl trithiocarbonate is added, the mixture is refluxed for 12 hours under the protection of nitrogen, cooled and filtered, washed by ethanol and dried in vacuum, thus obtaining the attapulgite AT-BTPT-2 with the surface modified trithiocarbonate chain transfer agent.
Adding 1g of AT-BTP-2 in the first step 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 azodiisobutyronitrile initiator and 0.09g S-benzyl S' -propyl trithiocarbonate as small molecule RAFT reagent to improve the controllability of polymerization, vacuumizing, introducing high-purity nitrogen, repeatedly operating for 3 times, controlling the temperature to 70 ℃ to react for 48 hours in a dark state under the protection of the nitrogen, enabling the reaction bottle to be in open contact with air to cool, stopping the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-2 with the surface modified with polyethylene glycol monomethyl ether and tertiary amine side chain polymers.
And thirdly, firstly adding 1g of AT-P-2 in the second step into 10mL of acetonitrile, performing ultrasonic dispersion, slowly adding 1g of 3-chloromethyl-5-nitrosalicylaldehyde 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-2 with the surface modified with polyethylene glycol monomethyl ether and nitrosalicylaldehyde side chain polymers.
Adding 1g of AT-PCS-2 in the step three into 30mL of ethanol, adding 1g of 3-mercaptoaniline, stirring AT the temperature of 50 ℃ for reaction for 12 hours, filtering, washing with acetone, and drying in vacuum to obtain the attapulgite AT-PSH-2 with the surface modified with the polymer containing polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base side chains, wherein the structural formula of the final product is as follows:
example 3:
firstly, the attapulgite is filtered by a 200-mesh sieve to remove impurities, then 0.15mol/L hydrochloric acid solution is added for mechanical stirring for 12 hours, wherein the solid-liquid mass volume ratio of the attapulgite after the sieving and the impurity removal to the hydrochloric acid solution is 1:30g/mL, finally, deionized water is used for washing to be neutral, and the mixture is dried and ground. 2g of pretreated attapulgite AT-3 is weighed, dispersed in 50mL of acetonitrile, and 4g S-benzyl S' -trimethoxy silicon propyl trithiocarbonate is added, the mixture is refluxed for 12 hours under the protection of nitrogen, cooled and filtered, washed by ethanol and dried in vacuum, thus obtaining the attapulgite AT-BTPT-3 with the surface modified trithiocarbonate chain transfer agent.
Adding 1g of AT-BTPT-3 in the first step 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 small molecule RAFT reagent to improve the controllability of polymerization, vacuumizing, introducing high-purity nitrogen, repeatedly operating for 3 times, controlling the temperature to 70 ℃ to react for 48 hours in a dark state under the protection of nitrogen, contacting the open end of a reaction bottle with air to cool, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the attapulgite AT-P-3 with the surface modified with polyethylene glycol monomethyl ether and tertiary amine side chain polymer.
And thirdly, firstly adding 1g of AT-P-3 in the second step into 30mL of acetonitrile, performing ultrasonic dispersion, slowly adding 0.5g of 3-chloromethyl-5-nitrosalicylaldehyde under the cooling condition of 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 with polyethylene glycol monomethyl ether and nitrosalicylaldehyde side chain polymers.
Adding 1g of AT-PCS-3 in the step three into 80mL of ethanol, adding 0.5g of 4-mercaptoaniline, stirring and reacting for 12 hours AT the temperature of 50 ℃, filtering, washing with acetone, and drying in vacuum to obtain the attapulgite AT-PSH-3 with the surface modified with the polymer containing polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base side chains, wherein the structural formula of the final product is as follows:
example 4:
firstly, the morphology of the attapulgite before and after modification is observed through TEM, the pretreated attapulgite AT-1 can be seen to be in a random orientation needle shape with the average diameter of about 50nm in FIG. 1a, and the TEM image of the final product AT-PSH-1 in FIG. 1b shows that the needle-shaped attapulgite is coated with a layer of polymer, and the morphology also becomes not very regular.
Example 5:
the adsorption amount of the AT-1 to different heavy metal ions is studied by taking the attapulgite AT-1 pretreated in the embodiment 1 as an experimental sample.
Preparing 300mg/L aqueous solution of zinc nitrate, magnesium nitrate, chromium nitrate, cobalt nitrate, manganese sulfate and mercury nitrate, transferring the solution into a 100mL conical flask, and adding pretreated attapulgite AT-1 into the solution, wherein the concentration of AT-1 is set to be 1mg/L. The pH was adjusted to 6.0 using a small amount of nitric acid with a mass fraction of 20% or an aqueous solution of sodium acetate with a mass fraction of 30%, respectively. The temperature was kept at 25℃and the suspension was shaken at 120rpm, after 12 hours the attapulgite adsorbent was removed by centrifugation. The concentration of heavy metal ions in the solution was detected by using an inductively coupled plasma method, the adsorption capacity was calculated, and the average value was obtained by repeating 3 times, and the result is shown in fig. 2.
The result shows that the pretreated attapulgite AT-1 has small adsorption quantity of zinc, magnesium, chromium, cobalt, manganese and mercury ions, the value is close to about 10mg/g, and the selective adsorption performance of mercury ions cannot be shown. Because of the low adsorption capacity, if attapulgite AT-1 is to be used directly for removal of heavy metal contaminants from a body of water, the amount of attapulgite required in the application will be large.
Example 6:
the polymer modified attapulgite material AT-PSH-1 prepared in the embodiment 1 is taken as an experimental sample, and the adsorption amount of the AT-PSH-1 on different heavy metal ions is studied. The experimental conditions were the same as in example 5 and the results are shown in FIG. 3.
The result shows that the polymer modified attapulgite material AT-PSH-1 has little difference in adsorption quantity of zinc, magnesium, chromium, cobalt and manganese ions, about 50mg/L, however, AT-PSH-1 has very high adsorption capacity of mercury ions, up to 276mg/L. Therefore, the polymer modified attapulgite material AT-PSH-1 shows high affinity for mercury ions.
Example 7:
the polymer modified attapulgite material AT-PSH-1 prepared in the embodiment 1 is taken as an experimental sample, and the adsorption amount of the AT-PSH-1 on two heavy metal ions in the mercury-containing binary mixed solution is studied. Preparing a mixed solution containing mercury binary heavy metal ions, wherein the mercury ions are derived from mercury nitrate, and the other ions are derived from zinc nitrate, magnesium nitrate, chromium nitrate, cobalt nitrate and manganese sulfate, wherein the concentrations of the two metal ions in the mixed solution are respectively 300mg/L, and other experimental conditions are the same as those in example 5, and the results are shown in figure 4.
The result shows that the polymer modified attapulgite material AT-PSH-1 has much higher mercury ion adsorption than the other heavy metal ion in a binary system. In a binary system, the adsorption quantity of mercury ions is more than 250mg/L, and the adsorption quantity of the other heavy metal ions is in the range of 30-40 mg/L due to competitive adsorption, so that the AT-PSH-1 has stronger selective adsorption to mercury ions.
Claims (5)
1. An attapulgite modified by a polymer containing sulfhydryl Schiff base side group, which is characterized in that: the lateral 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,refers to nano needle-like rod crystal of attapulgite, R 1 ，R 2 Respectively one of hydrogen atoms or methyl groups, wherein x and y are the average polymerization degree of two grafting monomers, n is determined by the repeating unit of polyethylene glycol on a side chain of the monomer, and the terminal mercapto group is positioned at any one of ortho-position, meta-position and para-position on a benzene ring;
the preparation method comprises the following specific steps:
step one, the attapulgite is filtered by a 200-mesh sieve to remove impurities, then 0.15mol/L hydrochloric acid solution is added to be mechanically stirred for 12 hours, finally deionized water is used for washing to be neutral, and the mixture is dried and ground. The pretreated attapulgite AT is weighed and dispersed in an organic solvent, S-benzyl S' -trimethoxy silicone propyl trithiocarbonate is added, reflux is carried out for 12 hours under the protection of nitrogen, cooling and suction filtration are carried out, ethanol is used for washing, vacuum drying is carried out, and the attapulgite AT-BTPT of the surface modified trithiocarbonate chain transfer agent is obtained, wherein the reaction formula of the synthesis steps is as follows:
adding the AT-BTPT in the first step into an organic solvent, performing ultrasonic dispersion, adding a side chain polyethylene glycol monomethyl ether macromonomer, a side chain tertiary amine monomer, an azo diisobutyronitrile initiator and a small amount of S-benzyl S' -propyl trithiocarbonate BPTT as a small molecule RAFT reagent to improve the controllability of polymerization, vacuumizing, introducing high-purity nitrogen, repeatedly performing operation for 3 times, controlling the temperature to be 70 ℃ and performing light-proof reaction for 48 hours under the protection of the nitrogen, enabling a reaction bottle to be exposed to air, cooling, stopping the reaction, performing suction filtration, washing with tetrahydrofuran, and performing vacuum drying to obtain the polymer modified attapulgite AT-P with the side chain bonded polyethylene glycol monomethyl ether and tertiary amine, wherein the reaction formula of the above synthesis steps is expressed as follows:
step three, firstly adding the AT-P in the step two into acetonitrile, carrying out ultrasonic dispersion, slowly adding 3-chloromethyl-5-nitrosalicylaldehyde 3-CS under the cooling condition of ice water bath, stirring AT room temperature for reaction for 24 hours, then carrying out suction filtration, washing with acetone, and carrying out vacuum drying to obtain the polymer modified attapulgite AT-PCS with the side chains bonded with polyethylene glycol monomethyl ether and nitrosalicylaldehyde, wherein the reaction type of the synthesis steps is as follows:
adding the AT-PCS in the step three into ethanol, adding mercaptoaniline, stirring AT the temperature of 50 ℃ for reacting for 12 hours, performing suction filtration, washing with acetone, and performing vacuum drying to obtain the polymer modified attapulgite AT-PSH with the side chains bonded with polyethylene glycol monomethyl ether and mercaptosalicylaldehyde Schiff base, wherein the reaction formula of the synthesis steps is as follows:
2. the thiol-schiff base-side group-containing polymer-modified attapulgite clay according to claim 1, wherein the polymer-modified attapulgite clay is characterized by: the solid-liquid mass volume ratio of the attapulgite subjected to sieving and impurity removal in the first step to the hydrochloric acid solution of 0.15mol/L is 1:15-30 g/mL; 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 1:15-40 g/mL; the mass of the S-benzyl S' -trimethoxysilylpropyl trithiocarbonate is 0.5-2 times of the mass of the AT.
3. The thiol-schiff base-side group-containing polymer-modified attapulgite clay according to claim 1, wherein the polymer-modified attapulgite clay is characterized by: 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 1:30-50 g/mL; the side chain polyethylene glycol monomethyl ether macromer 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 macromer 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 the 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 the mass of the AT-BTPT; the mass of the small molecule RAFT reagent BPTT is 4-6 times of that of the azo-bis-isobutyronitrile initiator.
4. The thiol-schiff base-side group-containing polymer-modified attapulgite clay according to claim 1, wherein the polymer-modified attapulgite clay is characterized by: the solid-liquid mass volume ratio of AT-P and acetonitrile in the step three is 1:10-30 g/mL; the mass of the 3-chloromethyl-5-nitro salicylaldehyde is 0.5-2 times of that of AT-P.
5. The thiol-schiff base-side group-containing polymer-modified attapulgite clay according to claim 1, wherein the polymer-modified attapulgite clay is characterized by: the solid-liquid mass volume ratio of the AT-PCS to the ethanol in the step four is 1:30-80 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 the mass of the AT-PCS.
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