CN102294231B - Molecularly imprinted fiber material and preparation method thereof - Google Patents
Molecularly imprinted fiber material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002657 fibrous material Substances 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 42
- -1 polypropylene Polymers 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 229920001002 functional polymer Polymers 0.000 claims abstract description 14
- 229920001519 homopolymer Polymers 0.000 claims abstract description 13
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 229920001155 polypropylene Polymers 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 229920000297 Rayon Polymers 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 6
- 238000003795 desorption Methods 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 238000001291 vacuum drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 8
- 229960001124 trientine Drugs 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229930024421 Adenine Natural products 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 229960000643 adenine Drugs 0.000 claims description 5
- GFFGJBXGBJISGV-UHFFFAOYSA-N adenyl group Chemical group N1=CN=C2N=CNC2=C1N GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical group [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 4
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 2
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 230000005855 radiation Effects 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The invention discloses a molecularly imprinted fiber material and a preparation method thereof. The matrix of the molecularly imprinted material is an organic fiber, specifically polypropylene, polytetrafluoroethylene, viscose, polyacrylonitrile or polyvinyl alcohol. The preparation method comprises the following steps of: radiating the matrix fibers after being preprocessed using cobalt 60 gamma rays, mixing the radiated fibers with a graft monomer, and after a grafting reaction, removing homopolymers from the fibers through extraction filtration, and then drying the fibers in vacuum, thereby obtaining grafted modified fibers; reacting the grafted modified fibers with a functional polymer or a functional monomer, after the completion of the reaction, washing away the non-reacted functional polymer or functional monomer on the surface of the fibers, and then adding the fibers to the solution of template ions or template molecules to absorb the template ions or the template molecules; after the absorption is saturated, performing cross-linking using a cross-linking agent, and after the reaction is ended, removing the template ions or the template molecule through desorption using a desorbent, thereby obtaining the molecularly imprinted fiber material. The fiber material of the invention has high mechanical strength, high thermal stability, high chemical stability, high absorption capacity and high selectivity.
Description
Technical field
The present invention relates to a kind of molecular engram fibrous material and its preparation method and application, is take fiber as matrix, further implements the technology that trace prepares the molecular engram fibrous material by the graft modification fiber surface.
Background technology
Molecular imprinting can design preparation has selective recognition reaction to target molecule material easily.Because have high selectivity, stablize, be easy to the advantage such as preparation, molecular engram material is widely used in fields such as chromatogram, drug delivery, catalyst, SPE, separation recovery.Yet the molecular engram material of the methods such as traditional polymerisation in bulk preparation is because mass transfer velocity is slow, identification point is remained in easily the medium shortcoming of matrix and limited its application by embedding, template.In order to overcome these deficiencies, can improve imprinting efficiency by the print identification point is distributed in material surface.Wherein a kind of method commonly used is by reducing the size of trace particle, such as preparation nanometer or micron trace particle, thereby making more print identification point near material surface.But small sized particles faces fluid resistance in actual applications increases sharply the problems such as difficult separation and recycling.Another method is by grafting or applies molecularly imprinted polymer is grafted to matrix surface that matrix commonly used mainly is various particles and film at present, however the shortcoming such as this class material exists adsorption capacity not high equally, and membrane penetrating can be poor, and circulation is low.
Compare with membrane material with particle, fibrous material has large specific area, short mass transfer distance, and little pressure drop separates easily and reclaims, and the advantage such as can use in a variety of forms.A large amount of studies show that, can introduce various functional polymers at fiber surface easily by glycerol polymerization, chemical modification.Therefore take fiber as matrix, by graft modification molecularly imprinted polymer is grafted to fiber surface, can effectively overcomes the problem that present molecular engram material exists.Still be difficult to find a suitable system to make the trace fiber both have high imprinting efficiency but prepare molecular engram material take fiber as matrix, have again high percent grafting.Reason is that trace often needs different reaction conditions with grafting, and the optimum condition that is suitable for trace often is unfavorable for obtaining high percent grafting.Just because of this, although the fiber base imprinted material has a lot of potential advantages, the molecular engram material that rarely prepares take fiber as matrix at present is especially take organic fibers such as polypropylene, polyacrylonitrile, polytetrafluoroethylene (PTFE) as matrix.
Summary of the invention
The object of the invention is to according to defects of the prior art, a kind of molecular engram fibrous material with high mechanical strength, thermal stability, chemical stability, high-adsorption-capacity, high selectivity and fast adsorption rate is provided.
Another object of the present invention provides the preparation method of above-mentioned molecular engram fibrous material.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of molecular engram fibrous material is take organic fiber as matrix, and described organic fiber is polypropylene, polytetrafluoroethylene (PTFE), viscose, polyacrylonitrile or polyvinyl alcohol.
The preparation method of above-mentioned molecular engram fibrous material, concrete steps are as follows:
(1) preliminary treatment: matrix fiber was soaked 2 days in acetone (can be alkali lye in the industry), filter vacuum drying;
(2) grafting: dried matrix fiber is carried out irradiation with the Co 60 gamma rays, behind irradiation, mix with grafted monomers solution, the weight of control fiber and the volume ratio (hereinafter referred to as bath raio) of grafted monomers solution are 1:10~1:50, and the concentration of grafted monomers is 10~80%, and the reaction time is preferred 2 ~ 10 h of 0.5~10h(), reaction temperature is 50~100 ℃, make fiber carry out graft reaction, after reaction finished, suction filtration was removed homopolymers, vacuum drying obtains the graft modification fiber;
(3) trace: with graft modification fiber and functional polymer or function monomer reaction, control functional polymer or function monomer concentration are 1~100%, reaction time 1~20h, 20~150 ℃ of reaction temperatures, the unreacted functional polymer of flush away fiber surface or function monomer after reaction finishes, then add absorption template ion or template molecule in the solution of template ion or template molecule, adsorb saturated after, crosslinked with crosslinking agent, crosslinker concentration is 0.1~30%, 20~100 ℃ of reaction temperatures, reaction time 0.5~10h removes template ion with the desorbing agent desorption after reaction finishes or template molecule obtains the molecular engram fibrous material.
The described grafted monomers of step (2) is acrylic acid, methyl methacrylate, GMA, acrylonitrile or acrylamide.
The solvent of the described grafted monomers solution of step (2) is methyl alcohol, water, DMF or oxolane.
Step can also add activator in (2), can obtain better effect, the preferred Mohr's salt of activator, formaldehyde or magnesium powder, the preferred nanometer Mg powder of magnesium powder.
The described graft modification fiber of step (3) and functional polymer or function monomer reaction are carried out in solvent, and described solvent is water, methyl alcohol, DMF, oxolane, chloroform, carrene or toluene.
The described functional polymer of step (3) or function monomer are polymine, polyacrylic acid, ethylenediamine, diethylenetriamine, triethylene tetramine, acrylamide, methacrylic acid or acrylic acid.
The described template ion of step (3) is Cu
2+, Zn
2+, Cd
2+, Ni
2+, Pb
2+, Hg
2+Deng toxic heavy metal or Ag
+, Au
3+Deng noble metal, described template molecule is adenine, Tea Polyphenols etc.
The described crosslinking agent of step (3) is epoxychloropropane, glutaraldehyde, divinylbenzene or GDMA.
Think ratio with prior art, the present invention has following beneficial effect:
The present invention is take organic fibers such as polypropylene as matrix, at first by the graft modification fiber surface, further makes functional polymer or function monomer in the presence of template ion and crosslinking agent reaction and at the fiber surface trace, preparation molecular engram fiber.Prepare the molecular engram fibrous material by method of the present invention and can fundamentally solve the existing deficiency of present molecular imprinting, obtain existing high mechanical strength, thermal stability and chemical stability, have again the molecular engram material of high-adsorption-capacity, high selectivity and fast adsorption rate, will promote greatly development and the application of molecular imprinting.
Description of drawings
Fig. 1. molecular engram fiber and non-trace fiber are to the absorption property analysis chart of copper ion.
The specific embodiment
Further explain the present invention below in conjunction with specific embodiment, but embodiment does not do any restriction to the present invention.
Embodiment 1
The pretreated polypropylene fibre that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With acrylic monomers and methyl alcohol by volume percentage be mixed with the uniform mixed solution of 150ml at 30: 70, by 1: 30 bath raio (weight: the volume) polypropylene fibre behind the adding 5g pre-irradiation, add the activator Mohr's salt by 5%, reaction is 6 hours under 60 ℃ of temperature, with the reacted graft fibres of methanol wash to remove homopolymers and unpolymerized grafted monomers, vacuum drying, calculating percent grafting is 200%.Graft fibres are added in the polymine methanol solution of 1wt.% and react 10h, then use washed with methanol, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 50%.The polymine graft fibres are joined in the copper nitrate solution of 100ppm, adsorb fiber to be added in the glutaraldehyde ethanolic solution of 10 % after saturated and react 6h, reaction joins flush away copper ion in the 0.1M hydrochloric acid solution with fiber, the molecular engram fiber that drying obtains after finishing.As shown in Figure 1, through after the trace, fiber is to Cu
2+Adsorption capacity never the 4mg/g of trace fiber bring up to the 120mg/g of trace fiber, illustrate molecular imprinting can the Effective Raise material to the adsorption capacity of target molecule.
Embodiment 2
The pretreated polypropylene fibre of 20g is put into tool plug conical flask, seal with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.In the acrylic acid/water mixed solution by 1: 30 bath raio (weight: volume) polypropylene fibre behind the 5g pre-irradiation is joined 10/90(v/v) %, reaction is 1 hour under 80 ℃ of temperature, with the reacted graft fibres of methanol wash to remove homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 100%.Graft fibres are added in the aqueous solution of 30wt.% polymine (PEI) and react 8h, then use washed with methanol, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 60%.The polymine graft fibres are joined in the zinc nitrate solution of 100ppm, adsorb fiber to be added in 10% the glutaraldehyde ethanolic solution after saturated and react 6h, reaction joins flush away zinc ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 80mg/g to the zinc ion adsorption capacity, selecting coefficient is 20.
Embodiment 3
The pretreated polyacrylonitrile fibre that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With acrylic monomers and methyl alcohol by volume percentage be mixed with uniform mixed solution at 20: 80, by 1: 30 bath raio (weight: the volume) polyacrylonitrile fibre behind the adding 5g pre-irradiation, add the activator Mohr's salt by 5%, reaction is 6 hours under 60 ℃ of temperature, with the reacted graft fibres of methanol wash to remove homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 100%.Graft fibres are added in the polymine methanol solution of 1wt.% and react 10h, then use washed with methanol, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 40%.The polymine graft fibres are added in the copper nitrate solution of 100ppm, adsorb fiber to be added in the 10% glutaraldehyde ethanolic solution after saturated and react 6h, reaction joins flush away copper ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 100mg/g to the copper absorption capacity, selecting coefficient is 40.
Embodiment 4
The pretreated viscose fiber that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With GMA monomer and N, dinethylformamide (DMF) by volume percentage is mixed with uniform mixed solution at 40: 60, by 1: 30 bath raio (weight: the volume) viscose fiber behind the adding 5g pre-irradiation, reaction is 6 hours under 70 ℃ of temperature, with the reacted graft fibres of methanol wash to remove homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 120%.Graft fibres are added in the DMF solution of 1wt.% polymine and react 10h, then use washed with methanol, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 20%.The polymine graft fibres are added in the copper nitrate solution of 100ppm, adsorb fiber to be added in the 0.1% epoxychloropropane ethanolic solution after saturated and react 6h, reaction joins flush away copper ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 60mg/g to the copper absorption capacity, selecting coefficient is 26.
Embodiment 5
The pretreated polytetrafluoroethylene fibre that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With GMA monomer and N, dinethylformamide by volume percentage is mixed with uniform mixed solution at 30: 70, by 1: 30 bath raio (weight: the volume) polytetrafluoroethylene fibre behind the adding 5g pre-irradiation, add activator magnesium powder by 1%, reaction is 6 hours under 60 ℃ of temperature, with the reacted graft fibres of oxolane suction filtration removing homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 80%.Graft fibres are added in the methanol solution of 1wt.% polymine and react 10h, then water flushing, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 20%.The polymine graft fibres are added in the copper nitrate solution of 100ppm, adsorb fiber to be added in the 0.1% epoxychloropropane ethanolic solution after saturated and react 6h, reaction joins flush away copper ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 30mg/g to the copper absorption capacity, selecting coefficient is 50.
Embodiment 6
With GMA monomer and oxolane by volume percentage be mixed with uniform mixed solution at 10: 90, by 1: 30 bath raio (weight: volume) add 5g viscose fiber (viscose fiber is pressed embodiment 5 method preliminary treatment), 0.05% H
2O
2/ [(NH
4)
2SO
4FeSO
46H
2O] chemical initiator, reaction is 6 hours under 60 ℃ of temperature, with the reacted graft fibres of oxolane suction filtration removing homopolymers and unconverted monomer, vacuum drying, the calculating percent grafting is 200%.Graft fibres are added in the diethylenetriamine solution react 10h, then water flushing, the unreacted diethylenetriamine of flush away.The diethylenetriamine graft fibres are added in the cadmium nitrate solution of 100ppm, adsorb fiber to be added in the 0.1% epoxychloropropane ethanolic solution after saturated and react 6h, reaction joins flush away cadmium ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 80mg/g to the cadmium sorption capacity, selecting coefficient is 22.
Embodiment 7
Acrylic monomers and water by volume percentage are mixed with in the uniform mixed solution at 20: 80, by 1: 30 bath raio (weight: the polypropylene fibre after volume) adding 5g processes, add activator formaldehyde by 5%, at 60 ℃ with UV initiated grafting reaction 6 hours, with the reacted graft fibres of methanol wash to remove homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 150%.Graft fibres are added in the methanol solution of 1wt.% polymine and react 10h, then use washed with methanol, the unreacted polymine of flush away, calculating the polymine percent grafting after dry is 70%.The polymine graft fibres are added in the copper nitrate solution of 100ppm, adsorb fiber to be added in the 10% glutaraldehyde ethanolic solution after saturated and react 6h, reaction joins flush away copper ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 90mg/g to the copper absorption capacity, selecting coefficient is 45.
Embodiment 8
The pretreated vinal that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With GMA monomer and N, dinethylformamide by volume percentage is mixed with uniform mixed solution at 40: 60, by 1: 30 bath raio (weight: the volume) polypropylene fibre behind the adding 5g pre-irradiation, reaction is 5 hours under 120 ℃ of temperature, with the graft fibres behind the oxolane washing reaction to remove homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 200%.Graft fibres are added in the triethylene tetramine solution react 10h, then use washed with methanol, the unreacted triethylene tetramine of flush away.The triethylene tetramine modified fibre is added in the nickel nitrate solution of 100ppm, adsorb fiber to be added in the 10% epoxychloropropane ethanolic solution after saturated and react 6h, reaction joins flush away nickel ion in the 0.1M hydrochloric acid solution with fiber after finishing, drying obtains the molecular engram fiber, be 130mg/g to the nickel ion adsorption capacity, selecting coefficient is 30.
Embodiment 9
With GMA monomer and oxolane by volume percentage be mixed with uniform mixed solution at 20: 80, by 1: 20 bath raio (weight: volume) 5g viscose fiber and above-mentioned mixed solution are put into tool plug conical flask together, seal with pellosil, with the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With the graft fibres behind the oxolane suction filtration mutual radiation removing homopolymers and unconverted monomer, vacuum drying, calculating percent grafting is 200%.Graft fibres are added in the triethylene tetramine solution react 10h, then water flushing, flush away is the triethylene tetramine of reaction.The triethylene tetramine graft fibres are added in the Tea Polyphenols solution of 100ppm, adsorb fiber to be added in the 0.1% epoxychloropropane ethanolic solution after saturated and react 6h, after reaction finishes, 15/85 (v/v) % water/ethanol elution Tea Polyphenols template molecule, drying obtains Tea Polyphenols trace fiber, is 68mg/g to the adsorption capacity of Tea Polyphenols.
Embodiment 10
The pretreated polypropylene fibre that takes by weighing 20g is put into tool plug conical flask, seals with pellosil.With the Co 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.2ml acrylic acid, 2ml acrylamide, 30 GDMAs, 2g adenine, 70ml chloroform are made into mixed solution, add the above-mentioned graft fibres of 1g after stirring 0.5h, 60 ℃ of reactions 3 hours, wash reacted graft fibres with water to remove homopolymers and unconverted monomer, further use acidic aqueous solution desorption adenine template, drying obtains the molecular engram fiber, and the percent grafting that calculates fiber is 120%, is 90mg/g to the adsorption capacity of adenine.
Claims (2)
1. the preparation method of a molecular engram fibrous material, concrete steps are as follows:
(1) preliminary treatment: matrix fiber is soaked in acetone, filter, vacuum drying, described matrix fiber is polypropylene, polytetrafluoroethylene (PTFE), viscose, polyacrylonitrile or polyvinyl alcohol;
(2) grafting: dried matrix fiber is carried out irradiation with the Co 60 gamma rays, behind irradiation, mix with grafted monomers solution, the ratio of the volume of control fibre weight and grafted monomers solution is 1:10~1:50, and the concentration of grafted monomers is 10~80%, and the reaction time is 0.5~10h, reaction temperature is 50~100 ℃, make fiber carry out graft reaction, after reaction finished, suction filtration was removed homopolymers, vacuum drying obtains the graft modification fiber;
(3) trace: with graft modification fiber and functional polymer or function monomer reaction, control functional polymer or function monomer concentration are 1~100%, reaction time 1~20h, 20~150 ℃ of reaction temperatures, the unreacted functional polymer of flush away fiber surface or function monomer after reaction finishes, then add absorption template ion or template molecule in the solution of template ion or template molecule, adsorb saturated after, crosslinked with crosslinking agent, crosslinker concentration is 0.1~30%, 20~100 ℃ of reaction temperatures, reaction time 0.5~10h removes template ion with the desorbing agent desorption after reaction finishes or template molecule obtains the molecular engram fibrous material.
2. preparation method according to claim 1 is characterized in that the described grafted monomers of step (2) is acrylic acid, methyl methacrylate, GMA, acrylonitrile or acrylamide.
3. preparation method according to claim 1 is characterized in that the solvent of the described grafted monomers solution of step (2) is methyl alcohol, water, DMF or oxolane.
4. preparation method according to claim 1 is characterized in that step (2) also adds activator, and described activator is Mohr's salt, formaldehyde or magnesium powder.
5. preparation method according to claim 1, it is characterized in that the described graft modification fiber of step (3) and functional polymer or function monomer the reaction in solvent, carry out, described solvent is water, methyl alcohol, DMF, oxolane, chloroform, carrene or toluene.
6. preparation method according to claim 1 is characterized in that the described functional polymer of step (3) or function monomer are polymine, polyacrylic acid, ethylenediamine, diethylenetriamine, triethylene tetramine, acrylamide, methacrylic acid or acrylic acid.
7. preparation method according to claim 1 is characterized in that the described template ion of step (3) is Cu
2+, Zn
2+, Cd
2+, Ni
2+, Pb
2+, Hg
2+, Ag
+Or Au
3+, described template molecule is adenine or Tea Polyphenols.
8. preparation method according to claim 1 is characterized in that the described crosslinking agent of step (3) is epoxychloropropane, glutaraldehyde, divinylbenzene or GDMA.
9. molecular engram fibrous material that obtains to 8 arbitrary described preparation methods according to claim 1.
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