CN101185853A - Preparation method and application of sulfonylureas herbicide molecular engram superfine fibre film - Google Patents
Preparation method and application of sulfonylureas herbicide molecular engram superfine fibre film Download PDFInfo
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Abstract
The invention discloses the preparation method of a sulfonylurea herbicide molecular imprinting ultra fine fiber membrane, which comprises the following steps: (1) mixing acrylonitrile, alkenyl metalloporphyrin, an auxiliary function monomer, an initiator and a solvent together for polymerization; (2) pouring the reaction solution into a non solvent after the polymerization for precipitation separation to get a polymer, then the non solvent is adopted to extract and dry the polymer after grinding and dissolving the dried polymer and template molecule after being mixed together in N, N-dimethylformamide to get an uniform solution; (3) electrostatic spinning is conducted to the uniform solution gotten by the step (2) and drying to get the sulfonylurea herbicide molecular imprinting ultra fine fiber membrane after washing and eliminating the template molecule. The molecular imprinting ultra fine fiber membrane prepared by the invention is characterized by high sensitivity, great adsorption capacity, high separation efficiency and so on and has practical value in the application of the sulfonylurea herbicide in environmental samples testing, separating and purifying.
Description
Technical field
The present invention relates to molecular imprinting.Be specifically related to a kind of preparation method and application of sulfonylureas herbicide molecular engram superfine fibre film.
Background technology
Sulfonylurea herbicide is a class highy potent herbicide of developing in the last thirty years, is widely used in cereal crop control broad leaved weed and some grassy weed.This class herbicide has high activity and high selectivity, and some kind longevities of residure are longer, and it is a spot of in soil residually can to produce poisoning to late stubble sensitive crop.Therefore, very important to the residual extraction of sulfonylurea herbicide, separation and effective detection.Molecular imprinting (Molecular Imprinting Technique), gas-chromatography, high performance liquid chromatography, biological detection, chemical detection or their GC-MS have obtained describing to some extent in " sulfonylurea herbicide residue detection analysis and research new development " (" fine-chemical intermediate " 2006,36 (1): 1-6)) of application in various degree to this Ou Xiaoming.Wherein, molecular imprinting has unique precordainment, identity and practicality, show good prospects for application in the separation of residues of pesticides with in detecting, to this Zhang Huiting, Ye Guibiao, Li Wenming, Pan Canping is at " application of molecular engram sensor technology in Pesticides Testing " (" Pesticide Science journal ", 2006,8 (1): describe to some extent 8-13).
The important foundation of molecular imprinting is the interaction between microsphere and the function monomer.The patent of being correlated with both at home and abroad at present concentrates on molecularly imprinted polymer preparation methods and the application thereof based on hydrogen bond action, is in the patent documentation of 1263777C, CN 200410049648.4 and CN200510003610.8 as publication number.
But single hydrogen bond action does not exist selectivity high and reduce even the problem of forfeiture in the aqueous phase recognition capability.In addition, bigger because sulfonylureas herbicide molecular is bigger at highly cross-linked molecularly imprinted polymer inside diffusional resistance, be difficult to satisfy the requirement of mass transfer velocity and adsorption capacity in the practical application.This shows, adopt the molecularly imprinted polymer material based on hydrogen bond action of conventional cross-linked polymeric method preparation in detecting the residual application of sulfonylurea herbicide, to have a lot of weak points at present.
Summary of the invention
The invention provides a kind of preparation method of sulfonylureas herbicide molecular engram superfine fibre film, the molecular engram superfine fibre film that obtains has efficient identification and high flux separating power to sulfonylureas herbicide molecular in the environmental samples.
A kind of preparation method of sulfonylureas herbicide molecular engram superfine fibre film comprises the steps:
(1) with acrylonitrile (AN), thiazolinyl metalloporphyrin, miscellaneous function monomer, initator and solvent; Carry out polymerisation under the nitrogen protection, 60～80 ℃ of polymeric reaction temperatures, polymerization reaction time are 6～24 hours;
The preferred tetraphenyl zinc protoporphyrin of described thiazolinyl metalloporphyrin methacrylate (MMAZnTPP sees structural formula (I)) or tetraphenyl zinc protoporphyrin Methacrylamide (MAAZnTPP sees structural formula (II)):
The weight ratio of described thiazolinyl metalloporphyrin and acrylonitrile is 0.1～10: 1.
Described miscellaneous function monomer is acrylic acid (AA), methacrylic acid (MAA) or trifluoromethyl acrylate (TFMAA).The weight ratio of miscellaneous function monomer and acrylonitrile is 0.1～1: 1.
Described initator is selected from azodiisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO); The weight ratio of initator and acrylonitrile is 0.005～0.02: 1.
Described solvent is N, dinethylformamide (DMF).
Volume (unit the is milliliter) ratio of the weight of acrylonitrile, thiazolinyl metalloporphyrin and miscellaneous function monomer (unit is gram) sum and solvent is 1: 4～40.
(2) after polymerisation finishes, pour reactant liquor in non-solvent precipitate and separate, obtain polymer, grind the back and adopt non-solvent extracting, drying, with dried polymer be dissolved in N after template molecule mixes, dinethylformamide obtains homogeneous solution;
Described non-solvent is a kind of or any more multiple than what mix in water, ethanol or the methyl alcohol.
Described template molecule is a sulfonylurea herbicide, be the herbicidal activity compound,, triasulfuron grand as metsulfuron-methyl, chlorine sulphur, triflusulfuronmethyl, tribenuron-methyl, fluorine third sulphur are grand, cinosulfuron, thifensulfuronmethyl, nicosulfuron, bensulfuron-methyl, amidosulfuron, rimsulfuron 25, primisulfuronmethyl, ethametsulfuron, chlorimuronethyl, sulfometuronmethyl, fluorine pyridine sulphur is grand or tetrazolium sulphur is grand etc.
The weight ratio of dried polymer and template molecule is 0.1～50: 1.
Gross weight of the mixture of dried polymer and template molecule (unit is gram) and N, the ratio of the volume of dinethylformamide (unit is milliliter) is 1: 4～25 (g/ml).
(3) homogeneous solution that step (2) is obtained carries out electrostatic spinning, makes the superfine fibre film of diameter in 50～200 nanometer range; The superfine fibre film that obtains is removed behind the template molecule with organic solvent and the washing of organic acid mixture dry, sulfonylureas herbicide molecular engram superfine fibre film.
The voltage of described electrostatic spinning is 10～30kV.
The flow velocity of described electrostatic spinning is 0.5～5mL/ hour.
The dash receiver of described electrostatic spinning is 10～30cm to the distance between the spinning head.
In described organic solvent and the organic acid mixture:
Organic solvent is a methyl alcohol.
Organic acid is formic acid or acetate.
Organic solvent and organic acid volume ratio are 5～20: 1, are preferably 9: 1.
The present invention also provides the sulfonylureas herbicide molecular engram superfine fibre film and the purposes of described method preparation.
Sulfonylureas herbicide molecular engram superfine fibre film can be used for detecting or the separation and purification environmental samples in sulfonylurea herbicide.
The method of the sulfonylurea herbicide in the testing environment sample comprises the steps:
Sulfonylureas herbicide molecular engram superfine fibre film is immersed in the environmental samples solution, adopts ultraviolet spectrometer to measure the absorption property of molecular engram superfine fibre film template molecule.
The method of the sulfonylurea herbicide in the separation and purification environmental samples comprises the steps:
Sulfonylureas herbicide molecular engram superfine fibre film is filled in the filter, then environmental samples solution is carried out isolated by filtration, select the non-template molecule in contrast.
Sulfonylureas herbicide molecular all contains nitrogenous fragrant heterocycle structure, can form stable axial metal-complexing effect with the thiazolinyl metalloporphyrin, therefore, the thiazolinyl metalloporphyrin as function monomer, can be strengthened the interaction between sulfonylurea herbicide template molecule and the function monomer.On the other hand, can prepare superfine fibre film, make imprinted sites have good accessibility with high-specific surface area and high porosity by electrostatic spinning technique.Therefore, can reach based on the molecular engram superfine fibre film of thiazolinyl metalloporphyrin coordination sulfonylurea herbicide is carried out single-minded identification and the purpose of separating.
Advantage of the present invention:
Thiazolinyl metalloporphyrin and the function of molecular engram monomer of using always are at present combined, introduced coordination, prepared molecular engram superfine fibre film has very strong recognition capability to template molecule, thereby has highly sensitive characteristics;
The fibre diameter of prepared molecular engram superfine fibre film is in 50～200 nanometer range, specific area is big, porosity height, hole connective good, template molecule in the environmental samples is easily near recognition site, therefore compares with present common imprinted polymer material to have higher adsorption capacity;
Prepared molecular engram superfine fibre film flux is big, separative efficiency is high.
Highly sensitive, characteristics such as adsorption capacity is big, separative efficiency height that the prepared molecular engram superfine fibre film of the present invention has, the sulfonylurea herbicide in mensuration and separation and purification environmental samples is with practical value in using.
The specific embodiment
Embodiment 1
Take by weighing 0.2g acrylonitrile (AN), 0.02g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g methacrylic acid (MAA), 0.002g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.02g template molecule metsulfuron-methyl, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of metsulfuron-methyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 2
Take by weighing 0.15g acrylonitrile (AN), 0.02g thiazolinyl metalloporphyrin MAAZnTPP, 0.1g methacrylic acid (MAA), 0.0016g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 1g template molecule chlorine sulphur is grand, is dissolved in 4.4mL DMF, is that 30kV, flow velocity are that 5mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 200 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the grand molecular engram superfine fibre film of chlorine sulphur.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 3
Take by weighing 0.16g acrylonitrile (AN), 0.04g thiazolinyl metalloporphyrin MAAZnTPP, 0.12g methacrylic acid (MAA), 0.002g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the ethanol, separation, extracting, drying, obtain polymer.The polymer that 0.5g is made mixes with 0.01g template molecule triasulfuron, be dissolved in 2.04mL DMF, at voltage is that 15kV, flow velocity are that 0.5mL/ hour, receiving range are electrostatic spinning under the condition of 30cm, makes the superfine fibre film that fibre diameter is 50 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 5: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of triasulfuron.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 4
Take by weighing 0.04g acrylonitrile (AN), 0.4g thiazolinyl metalloporphyrin MMAZnTPP, 0.04g methacrylic acid (MAA), 0.0008g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 70 ℃ under the nitrogen protection.Pour reactant liquor in second alcohol and water (volume ratio 1: the 2) mixed liquor precipitation, separation, extracting, drying, obtain polymer.The polymer that 0.08g is made mixes with 0.015g template molecule triflusulfuronmethyl, is dissolved in 2mLDMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 15cm at voltage, makes the superfine fibre film that fibre diameter is 70 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 20: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of triflusulfuronmethyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 5
Take by weighing 0.25g acrylonitrile (AN), 0.07g thiazolinyl metalloporphyrin MMAZnTPP, 0.15g methacrylic acid (MAA), 0.003g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 6 hours in 80 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.15g is made mixes with 0.015g template molecule tribenuron-methyl, is dissolved in 1.6mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 50 nanometers.Adopt the mixed solution of methyl alcohol and formic acid (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of tribenuron-methyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 6
Take by weighing 0.12g acrylonitrile (AN), 0.02g thiazolinyl metalloporphyrin MMAZnTPP, 0.08g methacrylic acid (MAA), 0.001 g AIBN, 1.1mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 12 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.07g is made mixes with 0.07g template molecule fluorine third sulphur is grand, is dissolved in 0.64mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 70 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the grand molecular engram superfine fibre film of fluorine third sulphur.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 7
Take by weighing 0.3g acrylonitrile (AN), 0.08g thiazolinyl metalloporphyrin MMAZnTPP, 0.03g methacrylic acid (MAA), 0.0015 g AIBN, 2.5mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.18g is made mixes with 0.04g template molecule cinosulfuron, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of cinosulfuron.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 8
Take by weighing 0.22g acrylonitrile (AN), 0.05g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g acrylic acid (AA), 0.002 g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.14g is made mixes with 0.02g template molecule thifensulfuronmethyl, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of thifensulfuronmethyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 9
Take by weighing 0.12g acrylonitrile (AN), 0.03g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g trifluoromethyl acrylate (TFMAA), 0.0015g AIBN; 1.0mL DMF mixes, and adds in the reactor; logical nitrogen 30 minutes reacted 24 hours in 80 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.015g template molecule nicosulfuron, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of nicosulfuron.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 10
Take by weighing 0.2g acrylonitrile (AN), 0.02g thiazolinyl metalloporphyrin MMAZnTPP, 0.18g methacrylic acid (MAA), 0.0002g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.With reactant liquor pour precipitation in water and methyl alcohol (volume ratio 1: the 2) mixed liquor into, separate, extracting, drying, obtain polymer.The polymer that 0.15g is made mixes with 0.03g template molecule bensulfuron-methyl, is dissolved in 2mLDMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of bensulfuron-methyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 11
Take by weighing 0.14g acrylonitrile (AN), 0.03g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g methacrylic acid (MAA), 0.002 g AIBN, 10.8mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 70 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the methyl alcohol, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.016g template molecule amidosulfuron, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of amidosulfuron.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 12
Take by weighing 0.18g acrylonitrile (AN), 0.05g thiazolinyl metalloporphyrin MMAZnTPP, 0.15g methacrylic acid (MAA), 0.002g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 70 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.02g template molecule rimsulfuron 25, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of rimsulfuron 25.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 13
Take by weighing 0.15g acrylonitrile (AN), 0.045g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g methacrylic acid (MAA), 0.002 g AIBN, 1.5mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.015g template molecule primisulfuronmethyl, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of primisulfuronmethyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 14
Take by weighing 0.2g acrylonitrile (AN), 0.05g thiazolinyl metalloporphyrin MMAZnTPP, 0.15g methacrylic acid (MAA), 0.004g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.02g template molecule ethametsulfuron, is dissolved in 3mLDMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of ethametsulfuron.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 15
Take by weighing 0.12g acrylonitrile (AN), 0.03g thiazolinyl metalloporphyrin MMAZnTPP, 0.1g methacrylic acid (MAA), 0.0015g AIBN, 1.2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.08g is made mixes with 0.01g template molecule chlorimuronethyl, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of chlorimuronethyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 16
Take by weighing 0.18g acrylonitrile (AN), 0.04g thiazolinyl metalloporphyrin MAAZnTPP, 0.12g methacrylic acid (MAA), 0.002g AIBN, 2mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.03g template molecule sulfometuronmethyl, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the molecular engram superfine fibre film of sulfometuronmethyl.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 17
Take by weighing 0.1g acrylonitrile (AN), 0.05g thiazolinyl metalloporphyrin MMAZnTPP, 0.07g methacrylic acid (MAA), 0.001g AIBN, 1mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 60 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.06g is made mixes with 0.01g template molecule fluorine pyridine sulphur is grand, is dissolved in 1.2mLDMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 100 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the grand molecular engram superfine fibre film of fluorine pyridine sulphur.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Embodiment 18
Take by weighing 0.25g acrylonitrile (AN), 0.06g thiazolinyl metalloporphyrin MMAZnTPP, 0.2g methacrylic acid (MAA), 0.003g BPO, 2.5mL DMF mixes, and adds in the reactor, and logical nitrogen 30 minutes reacted 24 hours in 70 ℃ under the nitrogen protection.Pour reactant liquor into precipitation in the water, separation, extracting, drying, obtain polymer.The polymer that 0.1g is made mixes with 0.03g template molecule tetrazolium sulphur is grand, is dissolved in 2mL DMF, is that 10kV, flow velocity are that 1mL/ hour, receiving range are electrostatic spinning under the condition of 20cm at voltage, makes the superfine fibre film that fibre diameter is 80 nanometers.Adopt the mixed solution of methyl alcohol and acetate (volume ratio 9: 1) to clean prepared superfine fibre film, until detecting less than template molecule in the maximum absorption wave strong point, use the washed with methanol superfine fibre film again, drying obtains the grand molecular engram superfine fibre film of tetrazolium sulphur.
The molecular engram superfine fibre film that makes is immersed in the environmental samples solution, and test the results are shown in Table 1 to the absorption property of template molecule.The molecular engram superfine fibre film that makes is filled in the filter, and test the results are shown in Table 2 to the isolated by filtration performance of environmental samples solution.
Table 1 different molecular trace superfine fibre film is to the absorption property test result of template molecule
| Numbering | The thiazolinyl metalloporphyrin | The miscellaneous function monomer | Template molecule | Absorption was than (%) in 1 hour | Absorption was than (%) in 2 hours | Absorption was than (%) in 4 hours | Absorption was than (%) in 12 hours |
| Embodiment 1 | MMAZnTPP | MAA | Metsulfuron-methyl | 85 | 88 | 92 | 98 |
| Embodiment 2 | MAAZnTPP | MAA | Chlorine sulphur is grand | 89 | 90 | 95 | 99 |
| Embodiment 3 | MAAZnTPP | MAA | Triasulfuron | 84 | 88 | 93 | 95 |
| Embodiment 4 | MMAZnTPP | MAA | Triflusulfuronmethyl | 88 | 92 | 95 | 99 |
| Embodiment 5 | MMAZnTPP | MAA | Tribenuron-methyl | 82 | 89 | 95 | 98 |
| Embodiment 6 | MMAZnTPP | MAA | Fluorine third sulphur is grand | 85 | 89 | 94 | 98 |
| Embodiment 7 | MMAZnTPP | MAA | Cinosulfuron | 86 | 90 | 95 | 99 |
| Embodiment 8 | MMAZnTPP | AA | Thifensulfuronmethyl | 82 | 87 | 90 | 94 |
| Embodiment 9 | MMAZnTPP | TFMAA | Nicosulfuron | 82 | 90 | 93 | 96 |
| Embodiment 10 | MMAZnTPP | MAA | Bensulfuron-methyl | 85 | 89 | 92 | 99 |
| Embodiment 11 | MMAZnTPP | MAA | Amidosulfuron | 87 | 91 | 95 | 97 |
| Embodiment 12 | MMAZnTPP | MAA | Rimsulfuron 25 | 86 | 89 | 94 | 96 |
| Embodiment 13 | MMAZnTPP | MAA | Primisulfuronmethyl | 83 | 88 | 94 | 98 |
| Embodiment 14 | MMAZnTPP | MAA | Ethametsulfuron | 89 | 94 | 97 | 99 |
| Embodiment 15 | MMAZnTPP | MAA | Chlorimuronethyl | 84 | 89 | 95 | 97 |
| Embodiment 16 | MAAZnTPP | MAA | Sulfometuronmethyl | 86 | 94 | 95 | 99 |
| Embodiment 17 | MMAZnTPP | MAA | Fluorine pyridine sulphur is grand | 87 | 90 | 94 | 99 |
| Embodiment 18 | MMAZnTPP | MAA | Tetrazolium sulphur is grand | 88 | 91 | 95 | 98 |
Table 2 different molecular trace superfine fibre film is to the separation and purification The performance test results of template molecule
| Numbering | The thiazolinyl metalloporphyrin | The miscellaneous function monomer | Template molecule | Template molecule absorption is than (%) | The non-template Molecular Adsorption is than (%) |
| Embodiment 1 | MMAZnTPP | MAA | Metsulfuron-methyl | 95 | 18 |
| Embodiment 2 | MAAZnTPP | MAA | Chlorine sulphur is grand | 94 | 23 |
| Embodiment 3 | MAAZnTPP | MAA | Triasulfuron | 98 | 21 |
| Embodiment 4 | MMAZnTPP | MAA | Triflusulfuronmethyl | 93 | 27 |
| Embodiment 5 | MMAZnTPP | MAA | Tribenuron-methyl | 94 | 22 |
| Embodiment 6 | MMAZnTPP | MAA | Fluorine third sulphur is grand | 96 | 25 |
| Embodiment 7 | MMAZnTPP | MAA | Cinosulfuron | 97 | 27 |
| Embodiment 8 | MMAZnTPP | AA | Thifensulfuronmethyl | 97 | 29 |
| Embodiment 9 | MMAZnTPP | TFMAA | Nicosulfuron | 97 | 22 |
| Embodiment 10 | MMAZnTPP | MAA | Bensulfuron-methyl | 95 | 26 |
| Embodiment 11 | MMAZnTPP | MAA | Amidosulfuron | 99 | 24 |
| Embodiment 12 | MMAZnTPP | MAA | Rimsulfuron 25 | 93 | 23 |
| Embodiment 13 | MMAZnTPP | MAA | Primisulfuronmethyl | 94 | 25 |
| Embodiment 14 | MMAZnTPP | MAA | Ethametsulfuron | 98 | 26 |
| Embodiment 15 | MMAZnTPP | MAA | Chlorimuronethyl | 98 | 22 |
| Embodiment 16 | MAAZnTPP | MAA | Sulfometuronmethyl | 94 | 27 |
| Embodiment 17 | MMAZnTPP | MAA | Fluorine pyridine sulphur is grand | 95 | 26 |
| Embodiment 18 | MMAZnTPP | MAA | Tetrazolium sulphur is grand | 92 | 18 |
Claims (10)
1. the preparation method of a sulfonylureas herbicide molecular engram superfine fibre film comprises the steps:
(1) with acrylonitrile, thiazolinyl metalloporphyrin, miscellaneous function monomer, initator and solvent; Carry out polymerisation under the nitrogen protection, 60～80 ℃ of polymeric reaction temperatures, polymerization reaction time are 6～24 hours;
Described miscellaneous function monomer is acrylic acid, methacrylic acid or trifluoromethyl acrylate;
Described initator is azodiisobutyronitrile or dibenzoyl peroxide;
Described solvent is N, dinethylformamide;
(2) after polymerisation finishes, pour reactant liquor in non-solvent precipitate and separate, obtain polymer, grind the back and adopt non-solvent extracting, drying, with dried polymer be dissolved in N after template molecule mixes, dinethylformamide obtains homogeneous solution;
Described non-solvent is a kind of or any more multiple than what mix in water, ethanol or the methyl alcohol;
Described template molecule is a sulfonylurea herbicide;
(3) homogeneous solution that step (2) is obtained carries out electrostatic spinning, makes the superfine fibre film of diameter in 50～200 nanometer range; The superfine fibre film that obtains is removed behind the template molecule dry with organic solvent and the washing of organic acid mixture, obtained sulfonylureas herbicide molecular engram superfine fibre film.
2. preparation method according to claim 1 is characterized in that: the thiazolinyl metalloporphyrin described in the step (1) is a tetraphenyl zinc protoporphyrin methacrylate, sees structural formula (I) or tetraphenyl zinc protoporphyrin Methacrylamide, sees structural formula (II):
3. preparation method according to claim 1 is characterized in that: the weight ratio of thiazolinyl metalloporphyrin described in the step (1) and acrylonitrile is 0.1～10: 1; The weight ratio of miscellaneous function monomer and acrylonitrile is 0.1～1: 1; The weight ratio of initator and acrylonitrile is 0.005～0.02: 1; The weight sum of acrylonitrile, thiazolinyl metalloporphyrin and miscellaneous function monomer and the volume ratio of solvent are 1: 4～40.
4. preparation method according to claim 1 is characterized in that: the non-solvent described in the step (2) is a kind of or any more multiple than what mix in water, ethanol or the methyl alcohol; Described template molecule is a sulfonylurea herbicide.
5. preparation method according to claim 1 is characterized in that: the weight ratio of dried polymer and template molecule is 0.1: 1～50: 1 in the step (2); The gross weight of the mixture of dried polymer and template molecule and N, the ratio of the volume of dinethylformamide is 1: 4～25g/ml.
6. preparation method according to claim 1 is characterized in that: the sulfonylurea herbicide described in the step (2) is that metsulfuron-methyl, chlorine sulphur are grand, triasulfuron, triflusulfuronmethyl, tribenuron-methyl, fluorine third sulphur are grand, cinosulfuron, thifensulfuronmethyl, nicosulfuron, bensulfuron-methyl, amidosulfuron, rimsulfuron 25, primisulfuronmethyl, ethametsulfuron, chlorimuronethyl, sulfometuronmethyl, fluorine pyridine sulphur is grand or tetrazolium sulphur is grand.
7. preparation method according to claim 1 is characterized in that: the voltage of the electrostatic spinning described in the step (3) is 10～30kV;
The flow velocity of described electrostatic spinning is 0.5～5mL/ hour;
The dash receiver of described electrostatic spinning is 10～30cm to the distance between the spinning head;
8. preparation method according to claim 1 is characterized in that: in organic solvent described in the step (3) and the organic acid mixture: organic solvent is a methyl alcohol, and organic acid is formic acid or acetate, and organic solvent and organic acid volume ratio are 5～20: 1.
9. the sulfonylureas herbicide molecular engram superfine fibre film of preparation method's preparation according to claim 1.
10. the application in the sulfonylurea herbicide of sulfonylureas herbicide molecular engram superfine fibre film according to claim 9 in detection or separation and purification environmental samples.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621926A (en) * | 2019-01-30 | 2019-04-16 | 福州大学 | A kind of pair of putrescine has the Nanowire d type molecular engram film and preparation method thereof of efficient selective |
| CN110376179A (en) * | 2019-07-25 | 2019-10-25 | 东南大学 | A kind of preparation method, application and the detection method of molecular engram nanofiber enhancing basilar memebrane |
| CN114875507A (en) * | 2022-04-28 | 2022-08-09 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of pyrethroid molecular imprinting electrostatic spinning membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621926A (en) * | 2019-01-30 | 2019-04-16 | 福州大学 | A kind of pair of putrescine has the Nanowire d type molecular engram film and preparation method thereof of efficient selective |
| CN110376179A (en) * | 2019-07-25 | 2019-10-25 | 东南大学 | A kind of preparation method, application and the detection method of molecular engram nanofiber enhancing basilar memebrane |
| CN110376179B (en) * | 2019-07-25 | 2022-03-29 | 东南大学 | Preparation method, application and detection method of molecularly imprinted nanofiber reinforced basement membrane |
| CN114875507A (en) * | 2022-04-28 | 2022-08-09 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of pyrethroid molecular imprinting electrostatic spinning membrane |
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