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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- CN102294231B CN102294231B CN 201110116079 CN201110116079A CN102294231B CN 102294231 B CN102294231 B CN 102294231B CN 201110116079 CN201110116079 CN 201110116079 CN 201110116079 A CN201110116079 A CN 201110116079A CN 102294231 B CN102294231 B CN 102294231B
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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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| CN102675506B (en) * | 2012-06-12 | 2013-12-11 | 福州大学 | 6-kinetin molecularly imprinted polymer and application thereof |
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| CN105080504B (en) * | 2015-09-13 | 2017-08-04 | 衢州学院 | A kind of processing method of fluorine ion surface imprinted polymer and its fluorinated water |
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| CN111041821B (en) * | 2019-11-29 | 2022-10-28 | 中国船舶重工集团公司第七一八研究所 | Method for preparing functional fiber by ring-opening grafting of functional compound through cyclic substance |
| CN111514861B (en) * | 2020-05-13 | 2022-07-05 | 天津工业大学 | Preparation method and application of tridentate ligand heavy metal ion imprinting material |
| CN112553880B (en) * | 2020-11-24 | 2022-03-01 | 东华大学 | Method for depositing metal oxide on surface of limited-time protective product based on polyolefin non-woven fabric and protective product prepared by method |
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| CN113089317B (en) * | 2021-03-18 | 2022-09-30 | 武汉纺织大学 | Aminopyridine modified biomass fiber surface imprinting adsorption material and preparation method thereof |
| CN114062576B (en) * | 2021-12-14 | 2023-08-25 | 北京普析通用仪器有限责任公司 | Molecularly imprinted electrostatic spinning fiber membrane, preparation method thereof, microfluidic chip and method for detecting zearalenone |
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