CN118904299B - Preparation method of multifunctional material for extracting uranium from seawater - Google Patents
Preparation method of multifunctional material for extracting uranium from seawater Download PDFInfo
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- CN118904299B CN118904299B CN202410947925.0A CN202410947925A CN118904299B CN 118904299 B CN118904299 B CN 118904299B CN 202410947925 A CN202410947925 A CN 202410947925A CN 118904299 B CN118904299 B CN 118904299B
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- 239000013535 sea water Substances 0.000 title claims abstract description 76
- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 64
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 37
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- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical group O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 1
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- WFACWTZLXIFJCM-UHFFFAOYSA-N 5-(chloromethyl)-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(CCl)C=C1C=O WFACWTZLXIFJCM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/28—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
- B01J20/28023—Fibres or filaments
-
- 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
- B01J20/28—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
- B01J20/28028—Particles immobilised within fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention takes fiber, fabric or non-woven fabric as a base material, the surface is coated with unsaturated quaternary ammonium cationic rubber containing cyano groups, then the unsaturated quaternary ammonium cationic rubber is subjected to graft copolymerization reaction initiated by an aqueous free radical initiator together with acrylonitrile, cyano group-containing diallyl ammonium ion monomers, polycyano-containing bis (diallyl ammonium) cross-linking agents and the like, and then the multifunctional seawater uranium extraction material of which the surface is grafted with amidoxime, quaternary ammonium cations, amino groups, carboxyl betaine or sulfobetaine is prepared through amidoxime reaction of hydroxylamine.
Description
Technical Field
The invention relates to a preparation method of a multifunctional material for extracting uranium from seawater, in particular to a multifunctional material for extracting uranium from seawater, which is grafted with amidoxime, quaternary ammonium cations, amino, carboxyl betaine or sulfobetaine on the surface, can be used for enriching and extracting uranium from seawater, and belongs to the field of functional materials.
Technical Field
For more than half a century, many developed ocean countries have made extensive research and development in the directions of problems such as uranium distribution state in seawater, technology and method for extracting uranium from seawater, materials required for extracting uranium from seawater, uranium extraction engineering from seawater, safety for extracting uranium from seawater, environment for extracting uranium from seawater, and benefits for extracting uranium from seawater. The key point of the seawater uranium extraction is the selective combination of the base material of the seawater uranium extraction material and uranium absorption ligands. The method requires high toughness and durability of the base material, high selectivity of ligand adsorption uranium, large adsorption uranium capacity, simple preparation method of the seawater uranium extraction material, convenient fixed use and recovery, energy saving and environmental protection of elution cycle, high economic benefit and the like. Theoretical studies and experiments for many years show that the combination of polymer silk fabrics and chelate uranium-absorbing ligands is a preferable design and preparation scheme of the seawater uranium extraction material. The earliest combination of polymer silk fabric and chelate uranium-absorbing ligand is directly amidoxime of polyacrylonitrile fiber. Amidoximation of polyacrylonitrile fibers has several drawbacks that are difficult to overcome. ① In order to improve the adsorption capacity of amidoxime polypropylene fibers, it is desirable that cyano groups on the surfaces of the polyacrylonitrile fibers are amidoxime as much as possible, however, excessive amidoxime polypropylene fibers have poor mechanical properties, the amidoxime groups contained in ② amidoxime polypropylene fibers have small degrees of freedom in three-dimensional space, are very difficult to form stable geometric complexes in a 2:1 or 4:1 ratio relative to uranyl cations or uranyl carbonate anions, are easily competed by Fe 3+、Ni2+、Zn2+、Cu2+ or VO 2+ and the like in seawater, the ③ amidoxime polypropylene fibers have low hydrophilicity, have slow complex adsorption with uranyl ions in seawater, and can reach saturated adsorption approximately 30-50 days, and ④ amidoxime polypropylene fibers are adhered or wrapped by marine microorganisms in a short time after being immersed in seawater, so that the function of adsorbing the uranyl ions is lost.
In order to find out the uranium extraction material and the production technology of the seawater, which meet the conditions of good adsorption selectivity to uranyl cations or uranyl carbonate anions, high adsorption rate, large saturated adsorption capacity, high hydrophilicity, large specific surface area in contact with seawater, high mechanical strength, high chemical stability, adhesion resistance to microorganisms in seawater, simple adsorption-desorption process, low recycling cost, durability, easy positioning in open seawater, easy recovery and elution, high operation efficiency and the like, people have continuously struggle. The research results of the multi-nationality scholars in Japan, the United states, china and the like comprehensively show that the functional monomers such as acrylonitrile, acrylic acid, itaconic acid or vinyl phosphonic acid and the like grafted on the surfaces of the fiber or non-woven fabrics taking polyethylene, polypropylene or polystyrene polymer materials as base materials are satisfactory 'polymer silk fabrics + chelate uranium-absorbing ligands'. Firstly, the yield of the synthetic polymer base materials such as polyethylene, polypropylene or polystyrene is large, the source is wide, the price is low, the chemical stability is high, the surface grafting has little influence on the mechanical property of the synthetic polymer base materials, secondly, the non-woven fabrics have high porosity and large specific surface area, and the process of hot pressing, shearing, curling, folding, kneading, braiding and the like is simple and convenient, so that the synthetic polymer base materials are suitable for the suction filtration of seawater when the synthetic polymer base materials are arranged in open seas at various depths in a net weaving, rope weaving, branches and leaves, kelp or seaweed-like manner. Besides amidoxime can be grafted with acrylonitrile, functional monomers containing ligands, such as ① acrylic acid, itaconic acid, unsaturated phosphoric acid/unsaturated phosphonic acid, unsaturated sulfobetaine, unsaturated phosphorylcholine or unsaturated carboxyl betaine, are selected for graft copolymerization, the functional groups can enhance the selective complexation of amidoxime on uranyl cations or uranyl carbonate anions, ② unsaturated quaternary ammonium salts or unsaturated phosphorylcholine can remarkably improve the surface hydrophilicity of the high polymer materials, realize hydrophilic contact of sea water and uranium extraction materials, can realize the aggregation of uranium acyl carbonate anions to the materials through electrostatic attraction of positive charges carried by the functional groups, realize the ion exchange aggregation and rapid aggregation of the materials and sea water, and can also enhance the adhesion and growth of the uranium extraction materials on the surfaces of the materials, and ③ fibers or the surfaces of non-woven fabrics are grafted with organic polyamines, so that the hydrophilicity and the uranium absorption capacity of the materials can be improved. In view of this, how to design a omnipotent type uranium extraction material from seawater and a simple and effective preparation method based on the existing research results is the key to improve the comprehensive benefit of uranium extraction from seawater at present.
Disclosure of Invention
The invention subject group members take fiber as base material, are soaked and coated by polyglycidyl acrylate, and then undergo ring-opening reaction of organic polyamine and glycidyl, ji Anji ammonium salt reaction of 5-chloromethylsalicylaldehyde and oximation reaction of hydroxylamine hydrochloride to prepare chelating ion exchange fiber with series side chains bearing quaternary ammonium cations, amidoxime and salicylaldoxime functional groups, which can be used as seawater uranium extraction material with marine biofouling resistance, see CN102500432B, CN102505480B, CN102631954B, CN102516425B. However, in the application test, it was found that the chelating ion exchange fiber with the series of side chains supporting quaternary ammonium cations, amidoxime and salicylaldoxime functional groups has poor durability of the ion exchange function in simulated seawater and low adsorption selectivity for heavy metal ions. Through examination, the ester bonds in the series of chelate ion exchange fiber structures are continuously hydrolyzed in the weak alkaline seawater to lose the bonded functional groups, the adsorption stability of heavy metal ions is not high, and meanwhile, the water swelling rate of the chelate ion exchange fibers is too high. The popular seawater uranium extraction material in recent years is polyethylene or polypropylene fiber and non-woven fabric thereof as base materials, and acrylonitrile and unsaturated functional monomers are grafted on the surface of the base materials through ultraviolet irradiation, gamma-radiation or plasma. However, the high-energy radiation grafting method without using chemical reagent is clean and environment-friendly, the problem of homopolymerization of acrylonitrile and unsaturated functional monomers is still not completely solved through the improved process of grafting after pre-radiation, and the continuous production process of radiation grafting of m 2 -level large-area substrates is limited.
In the past, amidoxime has been considered as the most effective chelating ligand for uranyl ion, so that eyes of people are tightly focused on the surface of a substrate as many grafted acrylonitrile or functional ligands as possible (some report that the grafting rate of acrylonitrile is as high as more than 500%), and the positioning effect of the substrate and the pulling effect of a polyacrylonitrile chain are ignored, so that the degree of freedom of two ortho-amidoxime converted by grafting acrylonitrile on the surface of the substrate is small in geometric space, and the method is not suitable for coordination complexation of 2:1 or 4:1 with uranyl ion, and therefore many results report that the utilization rate of the amidoxime chelating adsorption of uranyl ion on the surface of the substrate is very low. The inventors consider that the improvement of the degree of freedom of two amidoxime in ortho-position on the substrate surface is beneficial to the self-assembled stable coordination complex of the amidoxime and uranyl ions in a ratio of 2:1 or 4:1, and meanwhile, the electrostatic attraction effect of charges carried on the substrate surface on the uranyl ions is relied on, so that the substrate is in a wide-spread-net type to actively collect extremely low-concentration uranyl ions from wide sea water on the substrate surface, thereby generating the self-assembled stable coordination complex of the amidoxime and uranyl ions in a ratio of 2:1 or 4:1. The inventor creates the preparation technology and the scheme of the multifunctional material for extracting uranium from seawater by 'wide spread net and self-assembly'.
Based on the summary of the prior work, the inventor discovers that the method for preparing the multifunctional material for extracting uranium from seawater, which has the advantages of simple technical scheme, wide substrate adaptability, continuous production process and excellent functions and performances, is realized by using the halogenated rubber glue solution to carry out surface coating sizing on the substrate for extracting uranium from seawater and then carrying out quaternization and chelating group functionalization on the halogenated rubber coating. The chemical principle of the polymer of the multifunctional material for extracting uranium from seawater is that the main chain and the side chain of the outer surface layer of the halogenated rubber coating layer of ① contain a large number of C=C double bonds, the exposed C=C double bonds can be used as grafting polymerization reaction centers initiated by oil-soluble free radical initiators, and the C=C double bonds contained in the main chain and the side chain of the inner layer of the halogenated rubber coating layer of ② can be subjected to free radical vulcanization initiated by the oil-soluble free radical initiators or bonding crosslinking with the polymer chain of the substrate, so that the mechanical strength of the rubber coating layer is improved, and the bonding effect between the rubber coating layer and the substrate crosslinking enhancing interface bonding is enhanced. ③ The 3-bromo (or chloro) allyl unit in the halogenated rubber chain structure is easy to carry out quaternization reaction with N- (2-cyanoethyl) -N, N-diallyl amine to prepare unsaturated quaternary ammonium cationic rubber with cyano groups on the surface, the unsaturated quaternary ammonium cationic rubber with cyano groups on the surface can carry out graft copolymerization reaction initiated by an aqueous free radical initiator such as acrylonitrile, cyano-containing diallyl ammonium ion monomer, polycyano-containing bis (diallyl ammonium) cross-linking agent and the like to prepare rubber with cyano groups grafted on the surface, poly quaternary ammonium cation chain or poly betaine, and then carry out amidoxime reaction with hydroxylamine hydrochloride to prepare the multifunctional seawater uranium extraction material with the surface grafted with amidoxime, amino group, carboxyl betaine or sulfobetaine. From the above simple principle introduction, the professional can implement halogenated rubber coating on the substrate of the uranium extraction material from seawater, then implement free radical initiated vulcanization, crosslinking, copolymerization grafting of various active centers and other reactions, not only complete free radical vulcanization of the unsaturated rubber coating and bonding crosslinking enhancement between the unsaturated rubber coating and the substrate, but also introduce multifunctional hydrophilic, antibacterial, antifouling and chelating groups such as amidoxime, quaternary ammonium cation, amino, carboxyl betaine, sulfobetaine and the like on the surface of the uranium extraction material from seawater.
The specific preparation scheme of the multifunctional material for extracting uranium from seawater, which is simple in preparation method and excellent in performance, is described in detail as follows:
The halogenated rubber glue solution refers to a halogenated rubber solution prepared by dissolving one or more than two of brominated natural rubber, brominated butyl rubber, brominated nitrile rubber, brominated polybutadiene, chlorinated natural rubber, chlorinated butyl nitrile rubber or chlorinated polybutadiene in a solvent, or a halogenated rubber emulsion prepared by dispersing one or more than two of brominated natural rubber, brominated butyl rubber, brominated nitrile rubber, brominated polybutadiene, chlorinated natural rubber, chlorinated butyl nitrile rubber or chlorinated polybutadiene in water.
The substrate refers to one or more than two of fiber, fabric or non-woven fabric.
The fiber, fabric or nonwoven fabric refers to natural fiber which takes polysaccharide or protein as a basic raw material and fabric or nonwoven fabric which takes natural fiber as a main raw material and is processed, or synthetic fiber which takes synthetic material as a basic raw material and fabric or nonwoven fabric which takes synthetic fiber as a main raw material and is processed, or blend fiber, composite fabric or nonwoven fabric which takes natural fiber and synthetic fiber as a main raw material and is processed.
Wherein the synthetic material refers to one or more than two of polyethylene, polypropylene, polystyrene, polyvinylidene fluoride, polyvinyl chloride, polyester, polyacrylonitrile, polyurethane, polyamide and polyvinyl acetal.
From the technical scheme and the essence of the invention, the professional will already know that the surface of the fiber, fabric or non-woven fabric is coated with or sized by using the halogenated rubber glue solution, the purpose of the invention is to uniformly coat the surface of the fiber, fabric or non-woven fabric with a rubber coating, wherein the outer surface layer of the rubber coating contains 3-primary bromine (chlorine) allyl units or 3-Zhong Xiu (chlorine) allyl units, is easy to complete nucleophilic substitution reaction with N- (2-cyanoethyl) -N, N-diallyl amine at normal temperature, and realizes unsaturated quaternization on the surface of the rubber coating;
The intrinsic C=C double bond in the halogenated rubber coating also provides a free radical crosslinking reaction center for preparing the multifunctional seawater uranium extraction material, and in addition, free radical vulcanization of a rubber chain is carried out to strengthen the mechanical property of the rubber layer, in addition, the free radical crosslinking of the rubber chain and fibers, fabrics or non-woven fabrics can be initiated, and the strong polarity of halogen atoms or cyano groups in the rubber layer is matched to jointly strengthen the bonding strength of two interfaces between the rubber layer and the fibers, fabrics or non-woven fabrics, so that the guarantee is provided for guaranteeing the mechanical property of the multifunctional seawater uranium extraction material.
Further, the surface of the substrate may be subjected to a coating pretreatment under conditions where optimizing performance requirements are preferred. The coating pretreatment of the substrate surface refers to coating pretreatment of the substrate surface by using a polymer solution or a polymer emulsion, and aims to improve the interfacial adhesion strength of the halogenated rubber coating and the substrate.
Wherein the polymer solution or polymer emulsion refers to one of halogenated rubber solution, resorcinol-formaldehyde condensation resin solution or emulsion, epoxy resin solution or emulsion, or polyvinyl alcohol-formaldehyde condensation resin solution or emulsion, and the surface of the substrate is subjected to coating pretreatment.
The halogenated rubber solution used for coating pretreatment on the surface of the substrate is a halogenated rubber solution containing a fat-soluble initiator, and the amount of the fat-soluble initiator in the halogenated rubber solution containing the fat-soluble initiator is 0.05-5% of the mass of the halogenated rubber in the halogenated rubber solution containing the fat-soluble initiator.
Wherein the surface of the fiber, fabric or nonwoven fabric based on polyethylene, polypropylene or polystyrene must be pre-activated before the coating pretreatment. Wherein the surface preactivation treatment refers to one of an acidic oxidation treatment using an aqueous potassium permanganate solution, a plasma radiation treatment in an oxygen atmosphere, a radiation treatment in an air atmosphere, or a corona discharge treatment. After the surface of the fiber, fabric or non-woven fabric taking polyethylene, polypropylene or polystyrene as a basic raw material is pre-activated, groups such as-OH, -CHO or-COOH are introduced into the surface of the fiber, fabric or non-woven fabric, so that the adhesiveness of the surface of the substrate is improved, and the fiber, fabric or non-woven fabric has great significance in ensuring the firmness of the surface of the substrate, which is coated with halogenated rubber and then grafted with amidoxime, quaternary ammonium cation, amino, carboxyl betaine or sulfobetaine.
The N- (2-cyanoethyl) -N, N-diallyl amine is unsaturated tertiary amine containing cyano, and performs nucleophilic substitution reaction with the exposed 3-bromo (chloro) allyl structural unit of the halogenated rubber coating, and unsaturated quaternary ammonium cations are grafted on the rubber coating. The unsaturated quaternary ammonium cation grafted on the rubber coating is a quaternary ammonium cation monomer, participates in the graft copolymerization reaction initiated by an aqueous free radical initiator of acrylonitrile, cyano-containing diallyl ammonium ion monomer, polycyano-containing bis (diallyl ammonium) cross-linking agent and the like, and is a first reaction center established for realizing the grafting of amidoxime, amino, sulfobetaine or carboxyl betaine on the surface of the substrate. In order to satisfy both the presentation of the second reaction center and the free radical crosslinking of the rubber coating with the surface of the fiber, fabric or nonwoven, a fat-soluble initiator should be added to the halogenated rubber solution.
The cyano diallyl ammonium ion monomer has a structure shown in a general formula (I):
Wherein when Y in the general formula (I) is selected from substituted or unsubstituted C 1～C18 alkyl, X - is selected from Cl -、Br- or I -, and when Y is selected from-CH 2CH2CO2 -、-CH2CH2CH2CO2 - or-CH 2CH2CH2SO3 -, X - is not selected from any negative ion.
The polycyanobis (diallylammonium) crosslinking agent has a structure shown in a general formula (II):
Wherein in the general formula (II) Selecting C 1～C18 alkylene orX - is one of Cl -、Br-、I- or p-CH 3C6H4SO3 -, wherein n is a natural number between 0 and 200.
It is well known to those skilled in the art that dimethyldiallylammonium chloride is a commonly used cationic monomer, and its homopolymers, copolymers and graft polymers are widely used in water treatment, daily chemical industry, petroleum exploitation, paper industry and the like. In order to create more cationic monomers of the diallylammonium chloride type, one changes the dimethyl group into other hydrocarbon groups (for example butyl, hexyl, octyl, decyl, dodecyl, benzyl, etc.) or substituted hydrocarbon groups (carbobutoxyalkyl, etc.). The purpose is to meet different requirements, expand performance and function, and meanwhile, the copolymerization of related diallyl ammonium chloride and monomers such as allyl amine hydrochloride, diallyl amine hydrochloride, acrylamide, acrylic acid, methacryloyloxyethyl ammonium chloride, vinyl benzenesulfonic acid, vinyl phosphoric acid and the like is clear. Therefore, based on the earlier stage work of CN201110322472.5, CN201110322503.7, CN201110304602.2 and CN201110304603.7, the inventor based on the chemical principle of molecular design and based on the purpose and technical requirement of grafting acrylonitrile and functional monomers on the surface of the seawater uranium extraction material, disclosed in CN202311221445.8 are cyano-containing diallyl ammonium ion monomers, cyano-containing diallyl ammonium zwitterionic monomers and polycyano-containing bis (diallyl ammonium) cross-linking agents, which are applied to the surface grafting modification of polymer materials, and the seawater uranium extraction multifunctional material with excellent performance and comprehensive functions is prepared.
The specific preparation method of the multifunctional material for extracting uranium from seawater comprises the following steps:
Step one, preparation of unsaturated quaternary ammonium cationic rubber emulsion
The preparation method comprises the steps of weighing a solvent at room temperature, adding halogenated rubber into a reaction kettle under stirring, increasing the temperature of materials in the reaction kettle to 40-90 ℃ until the halogenated rubber is completely dissolved to obtain halogenated rubber solution, cooling the obtained halogenated rubber solution to the room temperature, adding a fat-soluble initiator into the obtained halogenated rubber solution, stirring uniformly to dissolve the obtained solution to obtain halogenated rubber solution containing the fat-soluble initiator for later use, adding N- (2-cyanoethyl) -N, N-diallyl amine into the halogenated rubber solution after nitrogen filling and deoxidization, carrying out heat preservation reaction for 12-20 hours, ending the reaction, carrying out negative pressure concentration to obtain a viscous fluid, stopping concentration, reducing the temperature of the materials in the reaction kettle to the room temperature, adding the fat-soluble initiator, continuously pumping the materials in the reaction kettle into an aqueous solution containing a surfactant after the fat-soluble initiator is dissolved, stirring to complete an emulsification process, and obtaining unsaturated quaternary ammonium cationic rubber emulsion containing the fat-soluble initiator for later use. The preparation of unsaturated quaternary ammonium cationic rubber is schematically represented by the reaction formula-1 by taking brominated rubber as an example:
Wherein the mass ratio of the halogenated rubber to the N- (2-cyanoethyl) -N, N-diallyl amine to the fat-soluble initiator to the solvent is 100:0.5-25:0.05-5:200-2000.
The halogenated rubber refers to one or more than two of brominated natural rubber, brominated butyl rubber, brominated nitrile rubber, brominated polybutadiene, chlorinated natural rubber, chlorinated butyl nitrile rubber or chlorinated polybutadiene.
The fat-soluble initiator refers to one or more than two of benzoyl peroxide, isopropyl benzene peroxide, 1, 3-bis (tert-butyl peroxyisopropyl) benzene, 1, 4-bis (tert-butyl peroxyisopropyl) benzene, lauroyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile or dioctyl azobisisobutyrate.
The solvent is selected from one or more than two of dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, n-butanol, isobutanol, tertiary butanol, tetrahydrofuran, 1, 4-dioxane, 2-methoxyethanol, 2-ethoxyethanol acetate, ethyl acetate, methyl acetate, butyl acetate, toluene, xylene, acetone, butanone, cyclohexanone, chlorobenzene, cyclohexane and petroleum ether.
The mass percentage of the surfactant in the aqueous solution is 0-5%, and the dosage of the aqueous solution is 0.5-2.5 times of the mass of the halogenated rubber.
Wherein the surfactant is one or more of sodium stearate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyoxyethylene nonylphenol ether-10, polyoxyethylene octylphenol ether-10 or polyoxyethylene sorbitan monooleate.
Step two, preparing a base material coated with unsaturated quaternary ammonium cationic rubber coating on the surface
At room temperature, placing the cleaned and surface-coated pretreated substrate into the unsaturated quaternary ammonium cationic rubber emulsion containing the fat-soluble initiator prepared in the first step for soaking or padding, or spraying or rolling the cleaned and surface-coated pretreated substrate to prepare the unsaturated quaternary ammonium cationic rubber emulsion containing the fat-soluble initiator, and then conveying the substrate which is uniformly dipped or uniformly coated with the unsaturated quaternary ammonium cationic rubber emulsion into a dryer to prepare the substrate with the surface coated with the unsaturated quaternary ammonium cationic rubber coating.
The dosage of the unsaturated quaternary ammonium cationic rubber emulsion is 0.05-5 times of the mass of the base material.
The substrate refers to one of a fiber, a fabric, or a nonwoven.
The fiber, the fabric or the non-woven fabric refers to one of natural fiber taking polysaccharide or protein as a basic raw material and fabric or non-woven fabric which is processed by taking the natural fiber as a main raw material, or one of synthetic fiber taking synthetic material as a basic raw material and fabric or non-woven fabric which is processed by taking the synthetic fiber as a main raw material, or one of blend fiber, composite fabric or non-woven fabric which is processed by taking natural fiber and synthetic fiber as a main raw material.
Wherein the synthetic material refers to one or more than two of polyethylene, polypropylene, polystyrene, polyvinylidene fluoride, polyvinyl chloride, polyester, polyacrylonitrile, polyurethane, polyamide and polyvinyl acetal.
The surface coating pretreatment of the substrate refers to coating pretreatment of the substrate surface with a solution of a polymer or an emulsion of a polymer. Wherein the solution or emulsion of the polymer is selected from one of a halogenated rubber solution containing an oil-soluble initiator, a solution of resorcinol-formaldehyde condensation resin or an emulsion of resorcinol-formaldehyde condensation resin, a solution of epoxy resin or an emulsion of epoxy resin, or a solution of polyvinyl alcohol-formaldehyde condensation resin or an emulsion of polyvinyl alcohol-formaldehyde condensation resin;
wherein the dosage of the polymer solution or the polymer solution is 0.05-5 times of the mass of the base material.
Wherein the halogenated rubber refers to one or more than two of brominated natural rubber, brominated butyl rubber, brominated nitrile rubber, brominated polybutadiene, chlorinated natural rubber, chlorinated butyl nitrile rubber or chlorinated polybutadiene.
The fat-soluble initiator in the halogenated rubber solution containing the oil-soluble initiator is selected from one or more than two of benzoyl peroxide, isopropyl benzene peroxide, 1, 3-bis (tert-butyl peroxyisopropyl) benzene, 1, 4-bis (tert-butyl peroxyisopropyl) benzene, lauroyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile or dioctyl azobisisobutyrate, wherein the fat-soluble initiator in the halogenated rubber solution containing the oil-soluble initiator is 0.05-5% of the mass of the halogenated rubber.
The preparation method of the halogenated rubber solution containing the oil-soluble initiator comprises the steps of weighing the halogenated rubber solution, cooling to room temperature, adding the fat-soluble initiator, stirring and dissolving to obtain the halogenated rubber solution containing the fat-soluble initiator for standby, wherein the use amount of the fat-soluble initiator in the halogenated rubber solution containing the fat-soluble initiator is 0.05-5% of the mass of halogenated rubber in the halogenated rubber solution.
Wherein the surface of the fiber, fabric or non-woven fabric which takes polyethylene, polypropylene or polystyrene as basic raw material is pre-activated before the surface coating pretreatment.
Wherein the surface pre-activation treatment method refers to one of an acidic oxidation treatment method using a potassium permanganate aqueous solution, a plasma radiation treatment method in an oxygen atmosphere, a gamma-ray radiation treatment method in an air atmosphere, or a corona discharge treatment method. Step three, preparing a surface grafted cyano group-containing polyquaternary ammonium cationic base material
Adding the base material of the surface-coated unsaturated quaternary ammonium cationic rubber coating prepared in the second step into a graft copolymer liquid, or spraying the graft copolymer liquid on the surface of the base material of the surface-coated unsaturated quaternary ammonium cationic rubber coating, or rolling the graft copolymer liquid on the surface of the base material of the surface-coated unsaturated quaternary ammonium cationic rubber coating, taking out the base material which is uniformly dipped or uniformly coated with the graft copolymer liquid, feeding the base material into a polymerization reactor, charging nitrogen, deoxidizing for 30 minutes, controlling the temperature to be 50-60 ℃ for carrying out oscillation polymerization for 4-8 hours, then raising the temperature to be 80-90 ℃ for carrying out oscillation polymerization for 2-4 hours, taking out the base material from the polymerization reactor, and cooling, washing and drying the base material to obtain the poly quaternary ammonium cationic base material with cyano grafted on the surface. Formula-2 schematically represents the structure of the surface grafted cyano-containing polyquaternary ammonium cationized substrate:
The grafting copolymer solution is prepared by mixing and dissolving acrylonitrile/cyano-containing diallylammonium ion monomer/polycyano-containing bis (diallylammonium) cross-linking agent/aqueous initiator in deionized water according to the mass ratio of 0-50:1-50:0.03-13:100, wherein the dosage of the grafting copolymer solution is 0.05-5 times of the mass of the surface-coated rubber coating substrate.
The cyano-containing diallylammonium ion monomer has a structure shown in a general formula (I):
Wherein when Y in the general formula (I) is selected from substituted or unsubstituted C 1～C18 alkyl, X - is selected from Cl -、Br- or I -, and when Y is selected from-CH 2CH2CO2 -、-CH2CH2CH2CO2 - or-CH 2CH2CH2SO3 -, X - is not selected from any negative ion.
The dicyano-containing bis (diallylammonium) cross-linking agent has a structure represented by the general formula (II):
Wherein in the general formula (II) Selecting C 1～C18 alkylene orX - is one of Cl -、Br-、I- and p-CH 3C6H4SO3 -, and n is a natural number between 0 and 200.
The water-based initiator is one or more than two of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, azo diisobutyl amidine hydrochloride, azo diiso Ding Mi hydrochloride, azo dicyanovaleric acid or azo diisopropyl imidazoline hydrochloride.
Step four, oximation reaction of surface grafting cyano group-containing polyquaternary ammonium cationized base material
Adding hydroxylamine salt into deionized water, stirring and dissolving, regulating the pH value to 6.0-8.5 by using alkali to prepare hydroxylamine aqueous solution, immersing the polyquaternary ammonium cationic substrate with cyano groups grafted on the surface, which is prepared in the step three, into the hydroxylamine aqueous solution, controlling the temperature to be 60-80 ℃, carrying out oscillating reaction for 10-12 hours, taking out the substrate after cooling, and carrying out washing and centrifugal spin-drying to obtain the multifunctional material for extracting uranium from seawater, wherein the formula 3 schematically expresses the structure of the multifunctional material for extracting uranium from seawater:
Wherein the hydroxylamine salt refers to hydroxylamine hydrochloride or hydroxylamine sulfate.
The alkali refers to one or more of sodium hydroxide, sodium carbonate, calcium oxide or magnesium oxide.
The dosage mass ratio of the surface grafted cyano-containing polyquaternary ammonium cationized substrate to the hydroxylamine salt to the deionized water is 1:0.5-5:1-5.
The invention provides the multifunctional material for extracting uranium from seawater, which has the beneficial effects that:
① By adopting the technical scheme of the invention, the multifunctional material for extracting uranium from seawater realizes the omnibearing uniform grafting of amidoxime, quaternary ammonium cation, tertiary amino, carboxyl betaine or sulfobetaine and other multifunctional ligands on the surface of the substrate, and the key point is that the grafting density can be manually regulated.
② The spacer arm for grafting the amidoxime on the surface of the multifunctional material for extracting uranium from seawater is relatively long, the amidoxime has high degree of freedom in a three-dimensional space, and a 2:1 or 4:1 geometric complex can be formed with uranyl ions or uranyl carbonate anions conveniently.
③ The multifunctional material for extracting uranium from seawater has high stability of various functional ligands such as amidoxime, quaternary ammonium cation, tertiary amino, carboxyl betaine or sulfobetaine on the surface of the multifunctional material in seawater or in an acid-base aqueous solution.
④ The surface of the multifunctional material for extracting uranium from seawater has high hydrophilicity, antibacterial property, marine organism fouling prevention, amphoteric ion double exchange characteristic and the like.
⑤ The base materials and reagent raw materials required for preparing the multifunctional material for extracting uranium from seawater are mainly industrial products, the raw materials are easy to obtain, the preparation method is simple, the cost is low, and the technological process is safe and efficient.
Detailed Description
The multifunctional material for extracting uranium from seawater and the preparation method thereof provided by the invention are further described by the following examples, and the purpose of the multifunctional material is to better understand the content of the invention. Therefore, the multifunctional materials for extracting uranium from seawater and the preparation method, which are not listed in the examples, should not be considered as limiting the scope of the present invention.
Example 1 preparation of multifunctional Polyacrylonitrile fiber-1
Step one, preparation of unsaturated quaternary ammonium cationic rubber emulsion
140 G of acetone and 60 g of tetrahydrofuran are weighed and put into a reaction kettle, 18 g of bromobutyl rubber (BIIR 2032, beijing Yanshan petrochemical industry Co., ltd., bromine mass percent content is 2.36%) is put into the reaction kettle after stirring, the temperature of the feed liquid in the reaction kettle is controlled to be 45-60 ℃, the bromobutyl rubber is dissolved to prepare a bromobutyl rubber solution after stirring for 6 hours, a mixture of 10 g of isobutanol and 1.02 g of N- (2-cyanoethyl) -N, N-diallylamine is added into the bromobutyl rubber solution under the protection of N 2, the reaction is kept for 12 hours, the reaction is ended, a low-boiling solvent is extracted under the negative pressure, at this time, the feed liquid in the reaction kettle is sticky, the temperature of the feed liquid in the reaction kettle is reduced to room temperature, the mixture of 1.8 g of azo-diisoheptonitrile and 6 g of isobutanol is added, after stirring uniformly, the feed liquid in the reaction kettle is continuously put into a 40 g of aqueous solution containing 0.6 g of polyoxyethylene sorbitol monooleate-10, and the emulsification process is completed after stirring, 74 g of bromoN- (2-cyanoethyl) -N, N-diallylammonium rubber is prepared.
And taking 20 g of the brominated butyl rubber solution, cooling to room temperature, adding 0.82 g of azobisisobutyronitrile, and stirring uniformly to obtain the brominated butyl rubber solution containing azobisisobutyronitrile for later use.
Step two, preparation of polyacrylonitrile fiber coated with unsaturated quaternary ammonium cationic rubber coating on surface
And (3) at room temperature, 20 g of cleaned and pre-activated polypropylene fibers are put into a brominated butyl rubber solution containing azobisisobutyronitrile prepared in the step one for padding 2-3 times, then the polyacrylonitrile fibers which are uniformly dipped with brominated butyl rubber glue solution are taken out and sent into a dryer, 22.8 g of the pre-treated polyacrylonitrile fibers coated with the brominated butyl rubber coating are prepared after drying, 22.8 g of the polyacrylonitrile fibers coated with the brominated butyl rubber coating are put into the brominated-N- (2-cyanoethyl) -N, N-diallylammonium rubber emulsion prepared in the step one for padding 2-3 times, then the polyacrylonitrile fibers which are uniformly dipped with brominated-N- (2-cyanoethyl) -N, N-diallylammonium rubber emulsion are taken out, and after natural drying and solidification, surfactants, solvents and the like are washed, and then 26.6 g of the polyacrylonitrile fibers coated with unsaturated quaternary ammonium cationic rubber coating are prepared after drying. Step three, preparing the surface grafted cyano-containing polyionization polyacrylonitrile fiber-1
Respectively weighing 2.5 g of N-benzyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallyl ammonium chloride, 2.5 g of 4- (N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallyl ammonium) butyrate, 1g of 1, 4-bis (N-bromo, N-diallyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) ammonium) butane and 0.55 g of azo diisobutyl amidine hydrochloride, mixing and dissolving in 16 g of deionized water to prepare a graft copolymer liquid, immersing 26.6 g of polyacrylonitrile fiber with the surface coated with the unsaturated quaternary ammonium cationic rubber coating prepared in the step two into the graft copolymer liquid for 2-3 times, charging nitrogen and deoxidizing for 0.5 hours, heating to 50-60 ℃, oscillating and polymerizing for 4 hours, lifting the temperature to 80-85 ℃, oscillating and extracting for 4 hours, washing the fiber after oscillating and extracting for 4 hours, and cooling for 2000 minutes after grafting and cooling for 2.58 minutes to obtain the polyacrylonitrile fiber with the surface coated with the unsaturated quaternary ammonium cationic rubber coating.
Thermogravimetric analysis revealed that the 58.2 g of the surface grafted cyano-containing polyionized polyacrylonitrile fiber-1 had a volatile content of 45.73% by mass, from which a grafting ratio ((58.2× 0.5427-26.6)/(26.6) ×100% = 18.7%) was calculated, wherein the grafting efficiency was (58.2× 0.5427-26.6)/(6.55=76.1%.
Step four, preparation of multifunctional polyacrylonitrile fiber-1 for extracting uranium from seawater
Adding 10g of hydroxylamine hydrochloride into 30mL of deionized water, regulating the pH value to 7.0-7.5 by using a caustic soda aqueous solution with the mass percentage concentration, immersing 58.2 g of the surface-grafted cyano-containing polyion polyacrylonitrile fiber-1 prepared in the step three, controlling the temperature to 60-80 ℃, carrying out oscillation reaction for 12 hours, taking out the fiber after cooling, washing to be neutral by water, and carrying out centrifugal spin-drying for 5 minutes at a constant speed of 2000+/-200 rpm to obtain 67.7 g of the multifunctional polyacrylonitrile fiber-1.
The thermogravimetric analysis shows that the volatile content of the multifunctional polyacrylonitrile fiber-1 is 45.18%, which means that the actual weight of 67.7 g of the multifunctional polyacrylonitrile fiber-1 is 37.8 g. At normal temperature, the material is immersed in artificial seawater containing uranyl nitrate, and the saturated adsorption time is 7.5 minutes and the saturated adsorption capacity is 147.5 mg/g. The initial contact angle of pure water of the multifunctional polyacrylonitrile fiber-1 is measured to be 37.3 degrees, and pure water drops completely infiltrate the fiber after 20 seconds, which proves that the contact angle of pure water of the multifunctional polyacrylonitrile fiber-1 prepared by the method is obviously reduced compared with that of the original polyacrylonitrile fiber by 112.5 degrees.
Comparative example 1 preparation of multifunctional Polyacrylonitrile fiber-2
According to the method and procedure of example 1, the graft copolymer solution was prepared by weighing 2.5 g of N-benzyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium chloride, 2.5 g of 4- (N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium) butyrate, 1g of 1, 4-bis (N, N-diallyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) ammonium) butane and 0.55 g of azobisisobutylamidine hydrochloride, respectively, mixing them with 15 g of deionized water, and "changing to" 1.5 g of N-benzyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium chloride, 1.5 g of 4- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) ammonium bromide, n-bis (2-cyanoethyl) amino) propyl) ammonium group) butane and azobisisobutylaminidine hydrochloride 0.55 g, were mixed in 15 g deionized water to prepare a graft copolymer solution "", 45.7 g of a surface-grafted cyano-containing polyion polyacrylonitrile fiber-2 was prepared. Thermogravimetric analysis revealed that the volatile content of the 45.7 g surface grafted cyano-containing polyionized polyacrylonitrile fiber-2 was 35.68% by mass, and the grafting ratio ((45.7x0.6432-23.5)/(23.5) ×100% = 25.1%) was calculated, wherein the grafting efficiency was (45.7x0.6432-23.5)/(6.55=90.7%.
Oximation reaction is carried out on the surface grafted cyano-containing polyion polyacrylonitrile fiber-2 by adopting oximation reaction conditions in the step four of the example 1, so as to obtain the multifunctional polyacrylonitrile fiber-2. At normal temperature, the saturated adsorption time of the multifunctional polyacrylonitrile fiber-2 to uranyl ions is measured to be 7.5 minutes, and the saturated adsorption capacity is measured to be 153.9 mg/g. The measured initial contact angle of the multifunctional polyacrylonitrile fiber-2 pure water is 32.5 degrees, and the pure water drops completely infiltrate the fiber after 20 seconds, which shows that the contact angle of the pure water of the multifunctional polyacrylonitrile fiber-2 is obviously reduced compared with that of the original polyacrylonitrile fiber by 112.5 degrees.
Comparative example 2 preparation of multifunctional Polyacrylonitrile fiber-3
According to the method and procedure of example 1, the graft copolymer solution was prepared by weighing 2.5 g of N-benzyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium chloride, 2.5 g of 4- (N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium) butyrate, 1g of 1, 4-bis (N, N-diallyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) ammonium) butane and 0.55 g of azobisisobutylammonium hydrochloride, respectively, mixing them with 15 g of deionized water, and "changing them to" 1.0 g of N-dodecyl-N- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) -N, N-diallylammonium chloride, 1.0 g of 3- (2-hydroxy-3- (N, N-bis (2-cyanoethyl) amino) propyl) ammonium chloride, respectively, n-bis (2-cyanoethyl) amino) propyl) ammonium group) methyl) benzene and azobisisobutylaminidine hydrochloride 0.55 g, were mixed in 15 g deionized water to prepare a graft copolymer solution, and 48.2 g of a surface-grafted cyano-containing polyion polyacrylonitrile fiber-3 was prepared. Thermogravimetric analysis revealed that the 48.2 g of the surface-grafted cyano-containing poly-ionized polyacrylonitrile fiber-3 had a volatile content of 38.14% by mass, from which a grafting ratio ((48.2x 0.6186-23.5)/(23.5) ×100% = 26.9%) was calculated, wherein the grafting efficiency was (48.2x 0.6186-23.5)/(6.55=96.4%).
Oximation reaction is carried out on the surface grafted cyano-containing polyion polyacrylonitrile fiber-3 by adopting oximation reaction conditions in the step four of the example 1, so as to obtain the multifunctional polyacrylonitrile fiber-3. At normal temperature, the saturated adsorption time of the multifunctional polyacrylonitrile fiber-3 to uranyl ions is measured to be 10.2 minutes, and the saturated adsorption capacity is measured to be 168.2 mg/g. The measured initial contact angle of the multifunctional polyacrylonitrile fiber-3 pure water is 32.5 degrees, and the pure water drops completely infiltrate the fiber after 20 seconds, which shows that the contact angle of the pure water of the multifunctional polyacrylonitrile fiber-3 is obviously reduced compared with that of the original polyacrylonitrile fiber by 112.5 degrees.
The comparative examples 1 and 2 are advantageous in improving grafting efficiency by increasing the proportion of the crosslinking agent used in the copolymer grafting solution as compared with the results of example 1.
Example 2 preparation of multifunctional Polypropylene nonwoven 1
According to the preparation method and the operation steps of the example 1, the pre-activated polyacrylonitrile fiber in the step two of the example 1 is changed into the pre-activated polypropylene melt-blown nonwoven fabric, so as to prepare the multifunctional polypropylene nonwoven fabric-1. The multifunctional polypropylene non-woven fabric-1 is immersed into artificial seawater containing uranyl nitrate, the saturated adsorption time is 10.3 minutes, the saturated adsorption capacity is 211.3 mg/g, the initial contact angle of pure water is 33.6 degrees, pure water drops completely infiltrate the multifunctional polypropylene non-woven fabric-1 after 20 seconds, and the pure water contact angle of the multifunctional polypropylene non-woven fabric-1 prepared by the method is obviously reduced compared with that of the original polypropylene melt-blown non-woven fabric by 122.4 degrees.
Comparative example 3 preparation of multifunctional Polypropylene nonwoven 2
According to the preparation method and the operation steps of the example 1, the polyacrylonitrile fiber preactivated in the step two of the example 1 is changed into 15.8 g of polypropylene melt-blown nonwoven fabric, and then the polypropylene melt-blown nonwoven fabric is immersed into the graft copolymerization solution of the step three of the example 1 as soon as possible after the preactivation treatment by gamma-ray irradiation in a dry air atmosphere, the temperature is controlled to 80 ℃ for 6 hours under the protection of N 2, and then the polypropylene melt-blown nonwoven fabric-2 with cyano groups grafted on the surface is prepared after cooling and water washing and centrifugal spin-drying for 5 minutes at a constant speed of 2000+/-200 rpm.
The thermal gravimetric analysis revealed that the volatile content of the 38.9 g of the surface-grafted cyano-containing polyionized polypropylene nonwoven fabric-2 was 38.44% by mass, and the grafting ratio was ((38.9× 0.6156-20)/(20) ×100% = 19.7%) (where grafting efficiency was (38.9× 0.6156-20)/(6.55= 60.26%). It is shown that the surface of the nonwoven can be modified by grafting cyano-containing polyions after pre-irradiation, but the grafting yield and grafting efficiency do not have a significantly improved effect.
The surface grafted cyano-containing polyionization polypropylene non-woven fabric-2 is immersed in the hydroxylamine aqueous solution in the fourth step of the example 1, and is subjected to oximation reaction, water washing and centrifugal drying for 5 minutes at a constant speed of 2000+/-200 rpm, so that 43.4 g of multifunctional polypropylene non-woven fabric-2 is obtained.
The thermogravimetric analysis showed that the volatile content of the multifunctional polypropylene nonwoven 2 was 38.32%, indicating that the actual weight of 43.4 grams of multifunctional polypropylene nonwoven 2 was 26.76 grams. At normal temperature, the material is immersed in artificial seawater containing uranyl nitrate, and the saturated adsorption time is measured to be 2.3 hours through a test, and the saturated adsorption capacity is 115.8 mg/g. The measured initial contact angle of pure water of the multifunctional polypropylene non-woven fabric-2 is 30.5 degrees, pure water drops completely infiltrate the non-woven fabric-2 after 25 seconds, which shows that the pure water contact angle of the multifunctional polypropylene non-woven fabric-2 prepared by the method disclosed by the invention is remarkably reduced compared with that of the original polypropylene melt-blown non-woven fabric by 122.4 degrees.
Comparative example 4 preparation of multifunctional Polypropylene nonwoven fabric-3
According to the preparation method and the operation steps of example 1, the pre-activated polyacrylonitrile fiber in the step two of example 1 is changed into 15.5 g of polypropylene non-woven fabric which is pre-activated by gamma-ray irradiation for 10 minutes in a dry air atmosphere, and is immersed in the graft copolymerization solution in comparative example 1 as soon as possible, the temperature is controlled to be 80 ℃ for 6 hours under the protection of N 2, and then the polypropylene non-woven fabric-3 with cyano grafted on the surface is prepared after cooling and water washing and centrifugal spin-drying for 5 minutes at a constant speed of 2000+/-200 revolutions per minute.
The thermal gravimetric analysis revealed that the volatile content of the 41.8 g of the surface-grafted cyano-containing polyionized polypropylene nonwoven fabric-3 was 38.61% by mass, and the grafting ratio ((41.8X 0.6139-20)/(20) ×100% = 28.3%) was calculated, wherein the grafting efficiency was (40.1X 0.6139-20)/(6.55=86.4%. The method for grafting the polypropylene non-woven fabric after pre-irradiation is described, the mass proportion of the cross-linking agent in the graft copolymerization solution is improved, and the grafting efficiency can be obviously improved.
41.8 G of the surface-grafted cyano-containing polyion polypropylene non-woven fabric-3 is immersed in the hydroxylamine aqueous solution in the fourth step of the example 1, and is subjected to oximation reaction, water washing and centrifugal drying for 5 minutes at a constant speed of 2000+/-200 rpm, so that 62.8 g of the multifunctional polypropylene non-woven fabric-3 is prepared.
The thermogravimetric analysis shows that the volatile content of the multifunctional polypropylene non-woven fabric-3 is 54.66 percent, which means that the actual weight of 62.8 grams of the multifunctional polypropylene non-woven fabric-3 is 28.49 grams. At normal temperature, the material is immersed in artificial seawater containing uranyl nitrate, and the saturated adsorption time is measured to be 2.5 hours through a test, and the saturated adsorption capacity is 113.1 mg/g. The measured initial contact angle of pure water of the multifunctional polypropylene non-woven fabric-3 is 31.3 degrees, pure water drops completely infiltrate the non-woven fabric-3 after 30 seconds, which shows that the contact angle of pure water of the multifunctional polypropylene non-woven fabric-3 prepared by the method disclosed by the invention is remarkably reduced by 122.5 degrees compared with that of the original polypropylene melt-blown non-woven fabric.
Example 3 preparation of multifunctional cotton gauze-1
According to the preparation method and the operation procedure of example 1, the pre-activated polyacrylonitrile fiber in the step two of example 1 was changed to 20.2 g of cotton absorbent gauze with the specification of 40×40 and the density of 50×50, and 76.7 g of the surface-grafted cyano-containing polyionization gauze-1 was prepared by the treatment processes of dipping the brominated butyl rubber solution containing azobisisobutyronitrile in the step one of example 1, the unsaturated quaternary ammonium cationic butyl rubber emulsion containing azobisisoheptonitrile, the graft copolymerization solution in the step three of example 1, and the like. The thermal gravimetric analysis revealed that the volatile content of 76.7 g of the surface-grafted cyano-containing polyionized gauze-1 was 54.07% by mass, and the grafting ratio ((81.7X 0.4593-32.4)/(32.4) ×100% = 15.8%) was calculated, wherein the grafting efficiency was (81.7X 0.4593-32.4)/(6.55=78.2%).
And (3) immersing the surface grafted cyano-containing polyionization gauze-1 into the hydroxylamine aqueous solution in the step four of the example 1 to complete the oximation reaction, and carrying out centrifugal drying for 5 minutes after washing with water at a constant speed of 2000+/-200 rpm to obtain 96.1 g of multifunctional all-cotton absorbent gauze-1.
Thermogravimetric analysis showed that the volatile content of 96.1 grams of multifunctional cotton absorbent gauze-1 was 60.37%, indicating that the actual mass of 96.1 grams of multifunctional cotton absorbent gauze-1 was 38.1 grams. At normal temperature, the material is immersed in artificial seawater containing uranyl nitrate, and the saturated adsorption time is measured to be 18.7 minutes through a test, and the saturated adsorption capacity is 193.6 mg/g. The multifunctional cotton absorbent gauze-1 is soaked after the pure water drops contact the cloth surface for 20 seconds after the initial contact angle of the pure water of the multifunctional cotton absorbent gauze-1 is measured to be 25.5 degrees, which proves that the multifunctional cotton absorbent gauze-1 prepared by the method has strong hydrophilicity.
Example 4 preparation of multifunctional cotton gauze-2
The brominated butyl rubber of step one of example 1 was changed to brominated polybutadiene in accordance with the preparation method and the procedure of example 1 to prepare a brominated polybutadiene solution containing benzoyl peroxide and an unsaturated quaternary ammonium cationic polybutadiene emulsion containing azobisisoheptonitrile, respectively.
The pre-activated polyacrylonitrile fiber in the second step is changed into 25g of cotton absorbent gauze with the specification of 40 multiplied by 40 and the density of 50 multiplied by 50, and 85.1 g of the surface-grafted cyano-containing polyionization gauze-2 is prepared through the treatment processes of dipping a brominated polybutadiene solution containing benzoyl peroxide, an unsaturated quaternary ammonium cationic polybutadiene emulsion containing azo-diisoheptonitrile, a graft copolymerization solution in the third step of the example 1 and the like. The thermal gravimetric analysis revealed that the percentage by mass of the volatile matters of the surface-grafted cyano-containing polyionized gauze-2 was 54.22%, from which a grafting ratio ((85.1× 0.4578-33.5)/(33.5) ×100% = 16.3%) was calculated, wherein the grafting efficiency was (85.1× 0.4578-33.5)/(6.55=83.3%.
And (3) immersing the surface grafted cyano-containing polyionization gauze-2 into the hydroxylamine aqueous solution in the step four of the example 1 to complete the oximation reaction, and carrying out centrifugal drying for 5 minutes after washing with water at a constant speed of 2000+/-200 rpm to obtain 101.7 g of multifunctional all-cotton absorbent gauze-2.
The thermogravimetric analysis showed that the volatile content of 101.7 g of multifunctional cotton absorbent gauze-2 was 60.37%, indicating that the actual mass of 101.7 g of multifunctional cotton absorbent gauze-2 was 40.3 g. At normal temperature, the material is immersed in artificial seawater containing uranyl nitrate, and the saturated adsorption time is measured to be 18.7 minutes by a test, and the saturated adsorption capacity is 113.8 mg/g. The multifunctional cotton absorbent gauze-2 is soaked after the pure water drops contact the cloth surface for 20 seconds after the initial contact angle of the pure water of the multifunctional cotton absorbent gauze-2 is measured to be 24.1 degrees, which proves that the multifunctional cotton absorbent gauze-2 prepared by the method has strong hydrophilicity.
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