CN104311824B - Magnetic polymer based on polymine and preparation method thereof - Google Patents
Magnetic polymer based on polymine and preparation method thereof Download PDFInfo
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- CN104311824B CN104311824B CN201410534892.3A CN201410534892A CN104311824B CN 104311824 B CN104311824 B CN 104311824B CN 201410534892 A CN201410534892 A CN 201410534892A CN 104311824 B CN104311824 B CN 104311824B
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Abstract
The present invention relates to magnetic polymer based on polymine and preparation method thereof; Utilizing linearity and branched polyethylene imine is macromolecular reaction thing, the method for rear modification synthesizing magnetic polymer. By polymine is quaternized, ion-exchange, then closes liron anion with four halogen and replaces the synthetic backbone chain type magnetic polymer with magnetic primitive of original anion. The molecular weight of polymer PEI used is at 600Da～1000kDa; Fe/N is 0.25～0.85. The polymine of different chain structures and molecular weight and iodomethane reaction are generated to quaternary ammonium salt, and quaternary ammonium salt reacts the synthetic polymer containing the primitive that is magnetic after ion-exchange with metal halide. The advantages such as the method has that cost is low, simple process, the gentle operating procedure of reaction condition are simple. This magnetic polymer is at magnetic film materials, electromagnetic device, absorbing material and CO2There is potential application the aspects such as separation and absorption.
Description
Technical field
The present invention relates to class magnetic polymer and a synthetic method thereof, particularly the magnetic polymer based on polymine andPreparation method; Utilizing linearity and branched polyethylene imine (PEI) is macromolecular reaction thing, the side of rear modification synthesizing magnetic polymerMethod.
Background technology
Polymine (PEI), as the highest large molecule of amino density, has unique physicochemical property, has therefore caused in a large number and has groundThe research interest of the person of studying carefully to it. (Boussifetal., the ProceedingsoftheNationalAcademyof such as BoussifSciences, 92 (16), 7297-7301.) find that PEI can be used as gene transfection agent. (the Beythetal.Biomaterials such as Beyth27 (2006) 3995 – 4002.) will be cross-linked quaternised PEI and sneak in medical resin, its antibacterial action is studied.Hu (Huetal., TheJournalofPhysicalChemistryB, 2005,109 (10): 4285-4289.) etc. adopt PEI modified carbonNanotube is also grown as substrate induction neuronal cell. (Sonetal., the MicroporousandMesoporous such as SonMaterials, 113 (1), 31-40.) PEI is implanted in porous silica material, explore its adsorption efficiency to CO2. VinogradovUtilize PEI to close as structure directing agent Deng (Vinogradovetal., MendeleevCommunications, 19 (4), 222-223.)Become porous C uO-Al2O3 composite. Nowadays, PEI has been widely used in the suction of gene transfection, anti-biotic material, CO2Enclosure material, multiple fields such as composite porous.
But up to this point, also someone utilizes PEI to modify synthesizing magnetic material. In recent years, magnetic high-molecularMaterial shows unique advantage in the field such as information industry and biomedical engineering. Separate at information storage material, magnetic especially,The aspects such as absorbing material, magnetic resonance imaging and medicine control release have tempting application prospect, are the focus classes of current researchOne of topic. Existing magnetic polymer material is roughly divided into two classes: a class is to mix the magnetic composite of inorganic particle;Another kind of is the magnetic high-molecular of being with the group that is magnetic on master chain. There is the poor problem of compatibility in the former, the latter often technique is multipleAssorted, cost is high. It is blank that the magnetic high-molecular synthetic method that preparation technology is simple, cost is relatively cheap and magnetic property is controlled still belongs to.This patent is by quaternized to PEI, ion-exchange, and composite iron salt, synthesizes for the first time and the magnetic that characterized based on PEI is divided greatlySon.
The document relevant to this patent be respectively: 2004, the Hyashi of Japan etc. (S.Hayashietal., ChemistryLetters,2004,33,1590-1591.) synthesize first and reported by quaternary ammonium salt cationic and tetrachloro close magnetic that iron anionic ion forms fromThe little molecule of sub-liquid. 2011, HispanicDeng (M.etal.,PolymerChemistry,2011,2,1275-1278.) reported first the preparation of closing the poly ion liquid of iron anion containing four halogen, by post-decoration method, polymer is enteredQuaternized and the anion exchange of row, thus compound four halogen close liron anion and prepare magnetic polymer afterwards.
Summary of the invention
The object of this invention is to provide a series of magnetic polymers based on polymine and preparation method thereof.
The technical scheme that technical solution problem of the present invention adopts:
Based on a magnetic polymer for polymine, it is to have following chemical structure of general formula:
Wherein the molecular weight of synthetic A, B PEI used is at 600Da～1000kDa; Fe/N is 0.25～0.85.
The synthetic method of polymer of the present invention, step is as follows:
(1) by molecular weight being dissolved in absolute ethyl alcohol at 600Da～1000kDa polymine, rub by N atom and iodomethaneYou are added drop-wise in iodomethane than 1:0.6～10; At 20～50 DEG C, stirring reaction finishes, and centrifugal to obtain solid water-soluble, at ethanolMiddle precipitation, centrifugal, vacuum drying, obtains intermediate product a;
(2) by soluble in water intermediate product a, in reaction system, add the chlorion exchanger resin excessive with respect to N atom, stirMix reaction and finish, filter, filtrate is revolved to steaming, vacuum drying obtains intermediate product b;
(3) solid b is dissolved in methyl alcohol, adds the FeCl with quaternized unit equivalent3·6H2O, stirring reaction finishes, and revolvesSteam, by product washing precipitation in ether, centrifugal, vacuum drying obtains target product magnetic polymer.
The synthetic method of magnetic polymer of the present invention, utilizing linearity and branched polyethylene imine is macromolecular reaction thing, rear modificationThe method of synthesizing magnetic polymer. The preparation of itself is by quaternized by polymine, and ion-exchange, then closes with four halogenLiron anion replaces the synthetic backbone chain type magnetic polymer with magnetic primitive of original anion. By by different chain structures andThe polymine of molecular weight and iodomethane reaction generate quaternary ammonium salt, and quaternary ammonium salt reacts and closes with metal halide after ion-exchangeBecome the polymer containing the primitive that is magnetic. Prepare by this method the backbone chain type different molecular weight with linearity and branched structureMagnetic polymer. The synthetic method that a kind of novel, feasible, efficient magnetic polymer is provided, the method has technique letterJust the feature that, cost is low, reaction condition is gentle. The magnetic polymer obtaining can be used as magnetic film materials, absorbing material andCO2Separate and sorbing material, than before material to have respectively cost low, magnetic is large, and the strong feature of stability.
Brief description of the drawings
The nuclear magnetic spectrum of Fig. 1 embodiment 1 polymer 1b;
Fig. 2 embodiment 1 magnetic polymer A1Raman collection of illustrative plates;
Fig. 3 embodiment 1 magnetic polymer A1Superconductive quantum interference collection of illustrative plates;
Fig. 4 embodiment 2 magnetic polymer A2Superconductive quantum interference collection of illustrative plates.
Fig. 5 embodiment 3 magnetic polymer A3Superconductive quantum interference collection of illustrative plates.
Fig. 6 embodiment 4 magnetic polymer B1Superconductive quantum interference collection of illustrative plates.
Fig. 7 embodiment 5 magnetic polymer B2Superconductive quantum interference collection of illustrative plates.
Fig. 8 embodiment 6 magnetic polymer B3Superconductive quantum interference collection of illustrative plates.
Detailed description of the invention
Contribute to further to understand the present invention by following example, but do not limit the present invention.
Embodiment 1
Magnetic polymer A1Synthetic:
(1) the linear PEI (270.8mg, 6.3mmol) of molecular weight 600Da is dissolved in 5ml absolute ethyl alcohol, is added drop-wise to iodine firstIn alkane (4ml, 64.2mmol). At 42 DEG C, stir 60h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble, at ethanolMiddle precipitation, centrifugal, vacuum drying, obtains intermediate product 1a.
(2), by soluble in water 1a (146.0mg, 1.0mmol), in system, add 4g chlorion exchanger resin stirring reaction 8h. CrossFilter, revolves steaming by filtrate, and vacuum drying obtains faint yellow solid 1b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 66%. AsFigure 1 shows that the nucleus magnetic hydrogen spectrum of 1b,1HNMR(500Hz,D2O) (multiplet, with quaternized list for chemical shift δ: 3.2-3.6Be connected-CH of unit2-,-CH3), 2.7-3.2 (multiplet, be connected with PEI unit-CH2-)。
(3) by 1b (83.2mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O (170.4mg, 0.633mmol) is moltenIn 5ml methyl alcohol, stir 16h, outstanding steaming, product washs with absolute ether, the centrifugal brown solid that obtains, vacuum drying obtains magneticProperty polymer A1. Figure 2 shows that magnetic polymer A1Raman collection of illustrative plates. 334cm in Raman collection of illustrative plates-1Place is FeCl4 -In ionThe absworption peak of Fe-Cl, conforms to document (S.Hayashietal., ChemistryLetters, 2004,33,1590-1591.). As Fig. 3Shown in magnetic polymer A1Superconductive quantum interference collection of illustrative plates be one and cross the straight line of initial point, illustrate that it has paramagnetism.
Embodiment 2
Magnetic polymer A2Synthetic:
(1) the linear PEI (268.7mg, 6.2mmol) of molecular weight 1000kDa is dissolved in 5ml absolute ethyl alcohol, is added drop-wise to iodineIn methane (3.9ml, 62.6mmol). At 50 DEG C, stir 100h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble,In ethanol, precipitate, centrifugal, vacuum drying, obtains intermediate product 2a.
(2), by soluble in water 2a (175.6mg, 1.0mmol), in system, add 4g chlorion exchanger resin stirring reaction 12h. CrossFilter, revolves steaming by filtrate, and vacuum drying obtains faint yellow solid 2b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 85%.
(3) by 2b (83.2mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O (170.4mg, 0.633mmol) is moltenIn 5ml methyl alcohol, stir 24h, outstanding steaming, product washs with absolute ether, the centrifugal brown solid that obtains, vacuum drying obtains magneticProperty polymer A2. Magnetic polymer A as shown in Figure 42Superconductive quantum interference collection of illustrative plates be one and cross the straight line of initial point, it is describedThere is paramagnetism.
Embodiment 3
Magnetic polymer A3Synthetic:
(1) the linear PEI (268.7mg, 6.2mmol) of molecular weight 10kDa is dissolved in 5ml absolute ethyl alcohol, is added drop-wise to iodine firstIn alkane (0.23ml, 0.37mmol). At 20 DEG C, stir 1h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble, in secondIn alcohol, precipitate, centrifugal, vacuum drying, obtains intermediate product 3a.
(2), by soluble in water 3a (82.1mg, 1.0mmol), in system, add 4g chlorion exchanger resin stirring reaction 12h. CrossFilter, revolves steaming by filtrate, and vacuum drying obtains faint yellow solid 3b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 25%.
(3) by 3b (59.1mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O (170.4mg, 0.633mmol) is moltenIn 5ml methyl alcohol, stir 24h, outstanding steaming, product washs with absolute ether, the centrifugal brown solid that obtains, vacuum drying obtains magneticProperty polymer A3. Magnetic polymer A as shown in Figure 53Superconductive quantum interference collection of illustrative plates be one and cross the straight line of initial point, it is describedThere is paramagnetism.
Embodiment 4
Magnetic polymer B1Synthetic:
(1) the side chain PEI (344.3mg, 8.0mmol) of molecular weight 0.18kDa is dissolved in 5ml absolute ethyl alcohol, slowly dripsIn iodomethane (2.5ml, 40.1mmol). At 40 DEG C, stir 48h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble,In ethanol, precipitate, centrifugal, vacuum drying, obtains intermediate product 4a.
(2), by soluble in water 4a (114.8mg, 1.0mmol), in system, add 4g chlorion exchanger resin stirring reaction 12h.Filter, solution is revolved to steaming, vacuum drying obtains faint yellow solid 4b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 46%.(3) by 4b (72.2mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O (124.4mg, 0.46mmol) is dissolved in5ml methyl alcohol, stirs 16h, outstanding steaming, and product obtains yellowish-brown solid with absolute ether washing precipitation, and it is poly-that vacuum drying obtains magneticCompound B1. Magnetic polymer B as shown in Figure 61Superconductive quantum interference collection of illustrative plates amplify after have a hysteresis curve, its tool is describedThere is ferromagnetism.
Embodiment 5
Magnetic polymer B2Synthetic:
(1) the side chain PEI (258.1mg, 6.0mmol) of molecular weight 10kDa is dissolved in 5ml absolute ethyl alcohol, is slowly added drop-wise toIn iodomethane (3.0ml, 60.0mmol). At 40 DEG C, stir 60h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble,In ethanol, precipitate, centrifugal, vacuum drying, obtains intermediate product 5a.
(2), by soluble in water 5a (139.8mg, 1.0mmol), in system, add 5g chlorion exchanger resin stirring reaction 12h.Filter, solution is revolved to steaming, vacuum drying obtains faint yellow solid 5b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 62%.
(3) by 5b (83.0mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O(124.4mg,0.46mmol)Be dissolved in 5ml methyl alcohol, stir 16h, outstanding steaming, product obtains yellowish-brown solid with absolute ether washing precipitation, and vacuum drying obtains magneticProperty polymer B2. Magnetic polymer B as shown in Figure 72Superconductive quantum interference collection of illustrative plates amplify after have a hysteresis curve, explanationIt has ferromagnetism.
Embodiment 6
Magnetic polymer B3Synthetic:
(1) the side chain PEI (266.5mg, 6.2mmol) of molecular weight 100kDa is dissolved in 5ml absolute ethyl alcohol, slowly dripsIn iodomethane (2.5ml, 40.1mmol). At 50 DEG C, stir 72h, reaction finishes that rear centrifugal to obtain yellow solid water-soluble,In ethanol, precipitate, centrifugal, vacuum drying, obtains intermediate product 6a.
(2), by soluble in water 6a (153.7mg, 1.0mmol), in system, add 4g chlorion exchanger resin stirring reaction 12h.Filter, solution is revolved to steaming, vacuum drying obtains faint yellow solid 6b, and obtaining quaternized conversion ratio by table 1 elementary analysis is 71%.
(3) by 6b (88.8mg, 1.0mmol) and with the FeCl of quaternized unit equivalent3·6H2O(124.4mg,0.46mmol)Be dissolved in 5ml methyl alcohol, stir 16h, outstanding steaming, product obtains yellowish-brown solid with absolute ether washing precipitation, and vacuum drying obtains magneticProperty polymer B3. Magnetic polymer B as shown in Figure 83Superconductive quantum interference collection of illustrative plates amplify after have a hysteresis curve, explanationIt has ferromagnetism.
Table 1
Above the present invention has been done to exemplary description, and nonrestrictive, the present invention is not limited to described in embodimentTechnology, authority is limited by claim, based on the art personnel according to the present invention can change, the method such as restructuring obtainsThe technology related to the present invention arriving, all within protection scope of the present invention.
Claims (3)
1. the magnetic polymer based on polymine, is characterized in that this magnetic polymer has following chemical structure of general formula:
Wherein the molecular weight of synthetic A, B polymine used is at 600Da～1000kDa; Fe/N mol ratio is 0.25～0.85.
2. the synthetic method of the polymer of claim 1, is characterized in that step is as follows:
(1) molecular weight is dissolved in absolute ethyl alcohol at the polymine of 600Da～1000kDa, rubs by N atom and iodomethaneYou are added drop-wise in iodomethane than 1:0.6～10; At 20～50 DEG C, stirring reaction finishes, and centrifugal to obtain solid water-soluble, at ethanolMiddle precipitation, centrifugal, vacuum drying, obtains intermediate product a;
(2) by soluble in water intermediate product a, in reaction system, add the chlorion exchanger resin excessive with respect to N atom, stirMix reaction and finish, filter, filtrate is revolved to steaming, vacuum drying obtains intermediate product b;
(3) solid b is dissolved in methyl alcohol, adds the FeCl with quaternized unit equivalent3·6H2O, stirring reaction finishes, and revolvesSteam, by product washing precipitation in ether, centrifugal, vacuum drying obtains target product magnetic polymer.
Described in claim 1 magnetic polymer of polymine prepare magnetic film materials, electromagnetic device, absorbing material andCO2Parting material and CO2The application of sorbing material aspect.
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| CN107163247A (en) * | 2017-05-25 | 2017-09-15 | 南京工业大学 | A kind of preparation method of linear polyamidoamine |
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| CN101781437A (en) * | 2010-01-12 | 2010-07-21 | 南京大学 | Magnetic acrylic acid series strongly basic anion exchange microballoon resin and preparation method thereof |
| CN102327768A (en) * | 2011-08-16 | 2012-01-25 | 湖南大学 | Imido magnetic nano-adsorbent as well as preparation method and application thereof |
| CN103992309A (en) * | 2014-05-30 | 2014-08-20 | 天津大学 | Side chain type magnetic monomer and polymer and controllable synthesis method thereof |
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| "Unique properties of polyaniline in the presence of applied magnetic field and ferric chloride";Shengqi Li et al;《Materials Chemistry and Physics》;20100612(第124期);第168-172页 * |
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