CN111944195A - Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof - Google Patents
Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof Download PDFInfo
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- CN111944195A CN111944195A CN202010812668.1A CN202010812668A CN111944195A CN 111944195 A CN111944195 A CN 111944195A CN 202010812668 A CN202010812668 A CN 202010812668A CN 111944195 A CN111944195 A CN 111944195A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 83
- 239000001913 cellulose Substances 0.000 title claims abstract description 83
- 239000004964 aerogel Substances 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 72
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002608 ionic liquid Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 125000000129 anionic group Chemical group 0.000 claims abstract description 19
- 239000000975 dye Substances 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 6
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005342 ion exchange Methods 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000000987 azo dye Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000004098 Tetracycline Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229960002180 tetracycline Drugs 0.000 claims description 4
- 229930101283 tetracycline Natural products 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- 150000003522 tetracyclines Chemical class 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001978 cystine tryptic agar Substances 0.000 claims 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UBMNMIBINYWHGZ-UHFFFAOYSA-M 1-ethenyl-3-[(4-ethenylphenyl)methyl]imidazol-3-ium;chloride Chemical compound [Cl-].C1=CC(C=C)=CC=C1CN1C=[N+](C=C)C=C1 UBMNMIBINYWHGZ-UHFFFAOYSA-M 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HSASKNPEYJOZHA-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-(1-hydroxy-2-oxo-2-phenylethyl)phenoxy]acetic acid Chemical compound C(=O)(O)COC=1C=C(C(C(C2=CC=CC=C2)=O)O)C=C(C=1)OCC(=O)O HSASKNPEYJOZHA-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- -1 hydrophobicity Substances 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002676 xenobiotic agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
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Abstract
The invention discloses a cellulose aerogel modified by polyion liquid and a preparation method and application thereof, wherein the cellulose aerogel CA-CTA modified by a chain transfer agent is reacted with an ionic liquid monomer and an initiator in DMSO at 50-80 ℃ in an inert gas atmosphere. According to the invention, hydroxyl on the surface of the cellulose aerogel is activated by carbonyl diimidazole CDI, hydrogenation esterification reaction is carried out on CA to obtain chain transfer agent CTA modified CA, and in-situ reversible addition fragmentation RAFT polymerization is carried out on the surface of CTA modified CA to obtain the PIL functionalized CA material with high polyion liquid PIL grafting amount. The reaction conditions are mild, the grafting rate is high, and the obtained cellulose aerogel has an adsorption effect on anionic dyes, aromatic ring functional groups or anionic antibiotics.
Description
Technical Field
The invention relates to a cellulose aerogel, in particular to a cellulose aerogel modified by polyion liquid and a preparation method and application thereof.
Background
The dye wastewater produced in various industries has the problems of high organic matter content, complex composition, deep color and the like, and is one of the accepted industrial wastewater which is difficult to control. The discharge of dye wastewater not only hinders the penetration of light, thereby affecting the biological processes in the water body, but also contaminates the groundwater and eventually enters the human body. Since most synthetic dyes are xenobiotics and carcinogens, potential health problems may arise. In addition, the structure of the dye is complex and stable, making it difficult and slow to degrade. Therefore, pretreatment of the dye in the wastewater is very important for environmental protection and public health.
At present, technologies based on membrane separation, adsorption, ion exchange, photocatalytic degradation, and reverse osmosis have been applied to the treatment of dye wastewater. As a method with low energy consumption, simple and convenient operation, high efficiency, high feasibility and safety and few byproducts, the adsorption technology is widely applied. The adsorption efficiency is mainly related to the structure of the adsorbent and adsorbate and other environmental factors. The key factor in determining high performance adsorption is the adsorbent material. However, the expensive precursors and the complex procedures involved in the synthesis hinder their practical application. Moreover, most raw materials used to make traditional sorbent materials are non-renewable and difficult to biodegrade. Therefore, for the purpose of sustainable development and environmental protection, development of low-cost, green and high-adsorptivity adsorbents derived from biomass materials is required.
Cellulose is the most abundant natural polysaccharide with good physical and mechanical properties as well as biocompatibility and degradability. Aerogels made from cellulose are ultra-light three-dimensional porous materials, combining the excellent properties of highly porous aerogels with sustainable biopolymers, are considered to be excellent candidates for the preparation of adsorbent materials. They are light in weight, have a high specific surface area, and have a porous structure, which helps expose more hydroxyl groups, thereby facilitating diffusion and penetration of guest molecules. Although Cellulose Aerogel (CA) itself has a certain adsorption effect, the low adsorption capacity is not satisfactory. This is due to the lack of chemical functional groups of native cellulose and interference with hydrogen bonding adsorption of hydroxyl groups in aqueous environments.
Disclosure of Invention
The invention aims to provide a polyion liquid modified cellulose aerogel and a preparation method and application thereof, solves the problem of poor cellulose adsorption effect, realizes CTA grafting by activating hydroxyl on the surface of the cellulose aerogel through CDI, and obtains a highly PIL modified CA material through in-situ RAFT polymerization to adsorb anionic dye, aromatic ring functional group-containing or anionic antibiotic.
In order to achieve the purpose, the invention provides a cellulose aerogel modified by polyion liquid, wherein the cellulose aerogel CA-CTA modified by a chain transfer agent is reacted with an ionic liquid monomer and an initiator in DMSO at 50-80 ℃ in an inert gas atmosphere.
Wherein the structure of the CA-CTA is:
R1any one selected from aromatic group, benzyl group and saturated alkane; w is selected from C or S; m is selected from saturated alkanes;
indicates the attachment location; n is 300 to 600.
The ionic liquid monomer is selected from any one of [ VBVIM ] Cl, [ MBVIM ] Cl and [ MBPVIM ] Cl:
preferably, the cellulose aerogel has a structure as shown in formula (1) or (2):
wherein,
preferably, the structure of X is shown as formula (2a) or (2 b):
in the formula (2a), R2Selected from benzyl or saturated alkanes; r3And R4Each independently selected from any one of H, methyl and cyano; m is 0-2; in the formula (2b), Ar is an aromatic group; r3And R4Each independently selected from any one of H, methyl and cyano; m is 0 to 2.
Preferably, the structure of X is shown as formula (2c) or (2 d):
in the formula (2c), R5Selected from methyl, carboxyl or phenyl; r3、R3’、R4And R4' each is independently selected from any one of H, methyl and cyano; m is 0-2; l is 0 to 11; in the formula (2d), R3And R4Each independently selected from any one of H, methyl and cyano; m is 0 to 2.
Preferably, X is selected from any one of the structures shown in formulas (2) to (10):
the invention also aims to provide a preparation method of the polyion liquid modified cellulose aerogel, and the synthesis route of the method is as follows:
the method comprises the following steps:
stirring and reacting compounds CA and CDI in anhydrous DMSO at 40-60 ℃ in an inert gas atmosphere under a dark condition to obtain a compound CA-CDI, then directly adding a compound CTA, and continuing to react to obtain the compound CA-CTA; and reacting CA-CTA, an ionic liquid monomer and an initiator in DMSO at 50-80 ℃ in an inert gas atmosphere to obtain the cellulose aerogel CA-g-PIL modified by the polyion liquid.
Wherein the Y anion is selected from Cl-、Br-、
When Y in the cellulose aerogel CA-g-PIL is not Cl-The method further comprises: an ion exchange step of subjecting the ionic liquid to ion exchangeIon exchange is carried out on the compound and salt solution containing Y anions, and RAFT polymerization is carried out on the compound and the compound CA-CTA; or carrying out ion exchange on the cellulose aerogel CA-g-PIL and a salt solution containing Y anions.
Wherein the CTA compound has the formula:
the ionic liquid monomer is selected from any one of [ VBVIM ] Cl, [ MBVIM ] Cl and [ MBPVIM ] Cl:
preferably, the mass ratio of the compounds CA and CDI is 1: 1; the molar ratio of the compound CDI to CTA was 1:0.8 to 2.0; the mass ratio of the ionic liquid monomer to the CA-CTA is (1-50): 1.
preferably, in the reaction system of the CA-CTA and the ionic liquid monomer, the dosage of DMSO is such that the concentration of the CA-CTA is 0.2-5 mg/mL; the initiator comprises: and the dosage of the azodiisobutyronitrile is 2-5% of the dosage of the ionic liquid monomer.
Preferably, the preparation of said compound CA comprises:
dissolving cotton linter pulp in NaOH/urea solvent at-12.5 ℃ to obtain a cellulose solution; and carrying out crosslinking reaction on the cellulose solution and Epoxy Chloropropane (ECH), standing, washing, and freeze-drying to obtain the compound CA.
The invention also provides application of the polyion liquid modified cellulose aerogel, which is characterized in that the polyion liquid modified cellulose aerogel is used for adsorbing anionic dyes, aromatic ring functional groups or anionic antibiotics; wherein the anionic dye comprises: anionic azo dyes; the antibiotic comprises: a tetracycline.
The polyion liquid modified cellulose aerogel, the preparation method and the application thereof solve the problem of poor cellulose adsorption effect, and have the following advantages: the cellulose aerogel modified by the polyion liquid has a strong adsorption effect on anionic dyes, aromatic ring functional groups or anionic antibiotics through PIL modification, imidazole PILs can perform various types of interaction with target adsorbates, including hydrophobicity, hydrogen bonds and static electricity, and the anionic dyes can be adsorbed through electrostatic interaction (even ion exchange) through positive charge imidazole salt functional groups in ionic liquid grafting layers in polymers, particularly azo dyes which contain benzene rings, naphthalene rings and the like, so that the adsorption is easily enhanced through pi-pi action, such as Congo red, AOII and the like. Antibiotics, which are anionic or contain aromatic ring functions, can be adsorbed by electrostatic action or pi-pi action.
According to the preparation method, hydroxyl on the surface of the cellulose aerogel is activated by CDI, hydrogenation esterification reaction is carried out on CA to obtain CTA modified CA, and in-situ RAFT polymerization is carried out on the surface of the CTA modified CA to obtain the PIL functionalized CA material with high PIL grafting amount. The reaction conditions of CTA modification (reaction at 40-60 ℃) and RAFT polymerization (reaction at 50-80 ℃) are mild, and the grafting rate is high. Whereas the CTA modification of existing cellulose is usually performed by esterification reactions, this requires higher reaction temperatures, which will result in some loss of mechanical properties of the modified CA. According to the invention, hydroxyl on the surface of the cellulose aerogel is activated by CDI, and the hydroxyl and CTA containing carboxyl have good reaction capability, so that the reaction can be carried out at a lower temperature, and the performance of the cellulose aerogel is not affected.
Drawings
FIG. 1 is a nuclear magnetic spectrum of 1- [ (4-vinylphenyl) methyl ] -3-vinylimidazolium chloride according to the invention.
FIG. 2 is a CA IR spectrum of the present invention.
FIG. 3 is an XPS spectrum of CA-CTA of the present invention.
FIG. 4 is an XPS spectrum of CA-g-PIL of the present invention.
Fig. 5 is a synthesis scheme of polyion liquid modified cellulose aerogels of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
A preparation method of a PIL modified cellulose aerogel comprises the following synthetic route:
wherein X is selected from any one of structures shown in formulas (2) to (10):
specifically, the preparation method comprises the following steps:
(1) synthesis of ionic liquid functional monomer IL
Vinylimidazole (VIM) and VBC or BCMBP or BCMB in a molar ratio of 1.1: 1 in a polar solvent under an inert gas atmosphere at 50 ℃. After the reaction was completed, the product was precipitated by ethyl ether, then purified by dissolution/precipitation (methanol/ethyl ether), and dried to finally obtain 1- [ (4-vinylphenyl) methyl ] -3-vinylimidazolium chloride (EVIM).
The polar solvent is selected from one or more of methanol, DMSO, DMF, acetonitrile and acetone.
TABLE 1 dosage of each reactant
(2) Preparation of pure Cellulose Aerogel (CA)
A cellulose solution (3 wt%) was obtained by dissolving cotton linter pulp (7 wt%/12 wt%, -12.5 ℃) in NaOH/urea solvent. To the cellulose solution was added 0.3mL of epichlorohydrin (ECH, which underwent a crosslinking reaction of the hydroxyl groups of cellulose), and after vigorous mixing, the solution mixture was poured into a mold and left to stand for 24 hours. After washing and freeze-drying for 2 days, the final Cellulose Aerogel (CA) was obtained.
Analysis of the prepared CA by Fourier Infrared Spectroscopy (FTIR) at 3313cm-1In the presence of OH, 1426cm-1Is positioned at 2870cm and is a sugar ring C-H-1Is represented by CH2，1019cm-1is-O-.
(3) Preparation of CTA-modified cellulose aerogel (CA-CTA):
first, the hydroxyl group of CA was activated with CDI (1,1' -carbonyldiimidazole), and CA (50mg) was immersed in a solution of 1 wt% CDI (CA: CDI ═ 1: 1w/w) in dry DMSO. N at 40 deg.C2Stirring for 24h under an atmosphere in the absence of light.
Then, a predetermined amount of CTA (CDI: CTA 1:0.8 mol/mol, CTA structure selected from any one of formulae (5 ') - (10') was added and mixed for another predetermined time, and CA was bound to the carboxyl group of CTA.
Finally, the modified CA was washed 3 times with DMSO and ethanol and vacuum dried at 40 ℃ for 48h to finally obtain CA-CTA.
(4) Preparation of polyion liquid (PIL) modified cellulose aerogel
Wherein,
AIBN (azodiisobutyronitrile) is used as an initiator, and the ionic liquid synthesized in the step (1) is used as a monomer and a cross-linking agent to carry out in-situ polymerization on the surface containing CA-CTA by using a RAFT polymerization technology, so that the polyion liquid graft modified cellulose aerogel (CA-g-PIL) with the structure shown in the formula (1) or (2) is generated.
Putting CA-CTA, an ionic liquid monomer (IL), AIBN and DMSO in a round-bottom flask, wherein the mass ratio of IL to CA-CTA is (1-50): 1, using the AIBN in an amount of 2-5% of the ionic liquid monomer, using the DMSO in an amount of 0.2-5 mg/mL to ensure that the CA-CTA is in concentration, reacting at 50-80 ℃ in a nitrogen atmosphere, and determining the reaction time according to the half-life period of the AIBN. After the reaction is finished, drying the obtained aerogel in vacuum to finally obtain CA-g-PIL.
In addition, if the ion exchange is required, the ion liquid functional monomer is subjected to ion exchange in advance and then polymerized; or directly carrying out ion exchange on the CA-g-PIL. Placing ionic liquid functional monomer or CA-g-PIL in salt solution containing Y anion (such as KBr, AgNO)3、NaBF4Or KPF6) Stirring at normal temperature, washing with deionized water after the exchange is finished, and drying to finish the ion exchange.
According to the method, hydroxyl on the surface of the cellulose aerogel is activated by CDI (1,1' -carbonyldiimidazole), hydrogenation esterification reaction is carried out on CA to obtain CTA modified CA, and in-situ RAFT polymerization is carried out on the surface of the CTA modified CA to obtain the PIL functionalized CA material with high PIL grafting amount. The reaction conditions of CTA modification (reaction at 40 ℃) and RAFT polymerization (reaction at 50-80 ℃) are mild, and the grafting rate is high.
Whereas the CTA modification of existing cellulose is usually performed by esterification reactions, this requires higher reaction temperatures, which will result in some loss of mechanical properties of the modified CA. According to the invention, hydroxyl on the surface of the cellulose aerogel is activated by CDI, and the hydroxyl and CTA containing carboxyl have good reaction capability, so that the reaction can be carried out at a lower temperature, and the performance of the cellulose aerogel is not affected.
Polyionic liquids (PILs) consist of a polymer backbone with ionic liquid species in the repeating unit, imidazole PILs can interact with target adsorbates in a variety of types, including hydrophobic (with hydrocarbon chains), hydrogen bonding (with imidazole rings), and electrostatic (due to ring charge). According to the invention, aiming at target dye molecules, an ionic liquid functional monomer (EVIM) with pi-pi interaction is selected, and in-situ RAFT polymerization is carried out on a CA surface modified by CTA, so that the PIL functionalized CA material with high PIL grafting amount is obtained. The PIL modified cellulose aerogel disclosed by the invention has excellent adsorption capacity on azo dye molecules and tetracycline antibiotics when being used as an adsorption material. Aiming at that the anionic dyes can be adsorbed by the positive charge imidazolium salt functional group in the ionic liquid grafting layer in the polymer through electrostatic action (even ion exchange); azo dyes in anionic dyes are a large class of dyes, contain benzene rings, naphthalene rings and the like, and are easier to enhance adsorption through pi-pi action, such as Congo red, AOII and the like. For antibiotics, it is desirable to be anionic or contain aromatic ring functionality, such as tetracycline.
The preparation process of the present invention is further illustrated by the following examples.
Example 1
A method of preparing a PIL-modified cellulose aerogel, the method comprising:
(1) synthesis of ionic liquid functional monomer
Vinylimidazole (4.14g, 0.044mol) and 4-chloromethylstyrene (6.105g, 0.040mol) were added to 10mL of methanol and stirred at 50 ℃ for 24h under nitrogen.
After the reaction was completed, the product was precipitated by using 200mL of diethyl ether, then purified twice by dissolution/precipitation (methanol/diethyl ether), and the residual solvent was removed by vacuum drying until constant weight, to finally obtain 1- [ (4-vinylphenyl) methyl ] -3-vinylimidazolium chloride (EVIM).
The nuclear magnetic characterization map of EVIM is shown in figure 1, and the characterization data is as follows:
1HNMR(DMSO,400MHz,ppm):9.96(a,1H),8.32(b,1H),8.03(c,1H),7.58-7.546(g+h,4H),7.42-7.32(d,1H),6.79-6.72(e,1H),6.06-6.01(e,1H),5.91-5.86(i,1H)5.51(f,2H),5.43-5.41(j,1H),5.32-5.29(j,1H)。
(2) preparation of Cellulose Aerogels (CA)
The cotton linter pulp was dissolved in NaOH/urea solvent (7 wt%/12 wt%) at-12.5 ℃ to obtain a 3 wt% cellulose solution. After 0.3mL of Epichlorohydrin (ECH) was added and mixed vigorously, the solution mixture was poured into a mold and allowed to stand for 24 h. After washing and freeze-drying for 2 days, the final Cellulose Aerogel (CA) was obtained.
The infrared spectrum of CA prepared by Fourier transform infrared spectroscopy (FTIR) analysis is shown in FIG. 2, 3313cm-1In the presence of OH, 1426cm-1Is positioned at 2870cm and is a sugar ring C-H-1Is represented by CH2，1019cm-1is-O-.
(3) Preparation of CTA-modified cellulose aerogels
Immersing the CA prepared in the step (1) into a DMSO solution of 1-5 wt% of CDI (CA: CDI ═ 1:1, w/w). At 40-60 ℃ and N2Stirring for 24h under an atmosphere in the absence of light. Thereafter, CTA (CDI: CTA 1:0.8, mol/mol) was added and mixed for a certain time. Then, it was washed 3 times with DMSO and ethanol, and vacuum-dried at 40 ℃ for 48 hours to obtain CTA-modified cellulose aerogel, CA-CTA.
CA-CTA prepared by FTIR analysis, 1758cm-1Is located at 3313cm of COO-1In the presence of OH, 1426cm-1Is positioned at 2870cm and is a sugar ring C-H-1Is represented by CH2，1019cm-1is-O-. The X-ray photoelectron spectroscopy (XPS) spectrum of CA-CTA is shown in FIG. 3.
(4) Preparation of PIL (polyion liquid) modified cellulose aerogel
About 20mg of CA-CTA, 400mg of ionic liquid monomer, 5mg of AIBN (azobisisobutyronitrile) and 5mL of LDMSO were added to a 25mL round-bottomed flask and kept at 70 ℃ for 3 hours under a nitrogen atmosphere.
After the reaction is finished, the obtained aerogel is washed by DMSO to remove unreacted monomers, is thoroughly washed by acetone, and is dried in vacuum at 40 ℃ for 48 hours to obtain the cellulose aerogel modified by the PIL, namely CA-g-PIL.
CA-g-PIL prepared by Fourier Infrared Spectroscopy (FTIR), 1577cm-1And 1538cm-1In the position of 1758cm and is an imidazole ring-1Is arranged asCOO，3313cm-1In the presence of OH, 1426cm-1Is positioned at 2870cm and is a sugar ring C-H-1Is represented by CH2，1019cm-1is-O-. The XPS spectrum of CA-g-PIL is shown in FIG. 4.
The formula for calculating the grafting ratio is as follows:
in the formula, mbAnd maRespectively, the dry weight of the compound to be grafted (e.g., CA-CTA) and the compound resulting from grafting (e.g., CA-CTA, CA-g-PIL).
The graft ratio (W, wt%) of CA was evaluated according to the above calculation formula, and in this example 1, the graft ratio of CTA was 30% and the graft ratio of PIL was 150%.
The procedure and results of the adsorption experiment for CA-g-PIL of example 1 are as follows:
10mgCA-g-PIL is taken and placed in 50mL azo dye congo red (500mg/L), the mixture is stirred for 24h at room temperature, the concentration of the solution before and after adsorption is obtained through an ultraviolet test, and the adsorption quantity is obtained by calculation and is 624 mg/g.
10mgCA-g-PIL is taken and placed in 200mL tetracycline (200mg/L), stirred for 24h at room temperature, the concentration of the solution before and after adsorption is obtained through ultraviolet test, and the adsorption quantity is calculated to be 461 mg/g.
Example 2
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 3
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 4
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 5
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 6
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 7
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 8
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: the CTA used in step (3) has the structure:
the structure of the obtained CA-g-PIL is as follows:
example 9
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: in step (3), CDI: the molar ratio of CTA was 1: 1.5.
CA-CTA prepared by FTIR analysis, 1752cm-1Is located at 3313cm of COO-1In the presence of OH, 1426cm-1Is positioned at 2870cm and is a sugar ring C-H-1Is represented by CH2，1019cm-1is-O-. According to infrared data, ester bond peaks which are characteristic peaks of successful grafting are all about 1750.
Example 10
A method of making a PIL-modified cellulose aerogel, substantially the same as example 1, except that: in step (3), CDI: the molar ratio of CTA was 1: 1.0.
CA-CTA, 1752COO, 3313cm prepared by FTIR analysis-1，OH，1426cm-1Sugar ring C-H, 2870cm- 1CH2，1019cm-1-O-。
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. The cellulose aerogel modified by the polyion liquid is characterized by being obtained by reacting cellulose aerogel CA-CTA modified by a chain transfer agent with an ionic liquid monomer and an initiator in DMSO at 50-80 ℃ in an inert gas atmosphere;
wherein the structure of the CA-CTA is:
R1any one selected from aromatic group, benzyl group and saturated alkane; w is selected from C or S; m is selected from saturated alkanes;
indicates the attachment location; n is 300-600;
the ionic liquid monomer is selected from any one of [ VBVIM ] Cl, [ MBVIM ] Cl and [ MBPVIM ] Cl:
2. the polyion liquid modified cellulose aerogel according to claim 1, wherein the cellulose aerogel has a structure represented by formula (1) or (2):
wherein,
and, in the formula (1), when
When yes, x is not equal to 0;
and, in the formula (2), R7Only is that:
3. the polyion liquid modified cellulose aerogel according to claim 1, wherein the structure of X is represented by formula (2a) or (2 b):
in the formula (2a), R2Selected from benzyl or saturated alkanes; r3And R4Each independently selected from any one of H, methyl and cyano; m is 0-2;
in the formula (2b), Ar is an aromatic group; r3And R4Each independently selected from any one of H, methyl and cyano; m is 0 to 2.
4. The polyion liquid modified cellulose aerogel according to claim 3, wherein X has the structure represented by formula (2c) or (2 d):
in the formula (2c), R5Selected from methyl, carboxyl or phenyl; r3、R3’、R4And R4' each is independently selected from any one of H, methyl and cyano; m is 0-2; l is 0 to 11;
in the formula (2d), R3And R4Each independently selected from any one of H, methyl and cyano; m is 0 to 2.
5. The polyion liquid modified cellulose aerogel according to claim 4, wherein X is selected from any one of the structures shown in formulas (2) to (10):
6. a method for preparing polyion liquid modified cellulose aerogel as claimed in any of claims 1-5, wherein the synthesis route of the method is as follows:
the method comprises the following steps:
stirring and reacting compounds CA and CDI in anhydrous DMSO at 40-60 ℃ in an inert gas atmosphere under a dark condition to obtain a compound CA-CDI, then directly adding a compound CTA, and continuing to react to obtain the compound CA-CTA;
reacting CA-CTA, an ionic liquid monomer and an initiator in DMSO at 50-80 ℃ in an inert gas atmosphere to obtain cellulose aerogel CA-g-PIL modified by polyion liquid;
wherein the Y anion is selected from Cl-、Br-、
Or
When the Y anion in the cellulose aerogel CA-g-PIL is not Cl ", the method further comprises: an ion exchange step of subjecting the ionic liquid monomer to ion exchange with a salt solution containing Y anions and then to RAFT polymerization with the compound CA-CTA; or carrying out ion exchange on the cellulose aerogel CA-g-PIL and a salt solution containing Y anions;
wherein the CTA compound has the formula:
the ionic liquid monomer is selected from any one of [ VBVIM ] Cl, [ MBVIM ] Cl and [ MBPVIM ] Cl:
7. the method for preparing polyion liquid modified cellulose aerogel according to claim 6, wherein the mass ratio of the compounds CA and CDI is 1: 1; the molar ratio of the compound CDI to CTA was 1:0.8 to 2.0; the mass ratio of the ionic liquid monomer to the CA-CTA is (1-50): 1.
8. the preparation method of the polyion liquid modified cellulose aerogel as claimed in claim 6, wherein in the reaction system of CA-CTA and ionic liquid monomer, the amount of DMSO is such that the concentration of CA-CTA is 0.2-5 mg/mL; the initiator comprises: and the dosage of the azodiisobutyronitrile is 2-5% of the dosage of the ionic liquid monomer.
9. The method for preparing polyion liquid modified cellulose aerogel according to claim 6, wherein the preparation of compound CA comprises:
dissolving cotton linter pulp in NaOH/urea solvent at-12.5 ℃ to obtain a cellulose solution;
and carrying out crosslinking reaction on the cellulose solution and epoxy chloropropane, standing, washing, and freeze-drying to obtain the compound CA.
10. Use of a polyion liquid modified cellulose aerogel according to any of claims 1 to 5, wherein the polyion liquid modified cellulose aerogel is used for adsorption of anionic dyes, aromatic ring containing functional groups or anionic antibiotics; wherein the anionic dye comprises: anionic azo dyes; the antibiotic comprises: a tetracycline.
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