CN107663194A - The halogen of alkyl imidazole four closes biphenyl type magnetic liquid crystal monomer of molysite substitution and preparation method thereof - Google Patents

The halogen of alkyl imidazole four closes biphenyl type magnetic liquid crystal monomer of molysite substitution and preparation method thereof Download PDF

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CN107663194A
CN107663194A CN201610622869.9A CN201610622869A CN107663194A CN 107663194 A CN107663194 A CN 107663194A CN 201610622869 A CN201610622869 A CN 201610622869A CN 107663194 A CN107663194 A CN 107663194A
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liquid crystal
intermediate product
molysite
halogen
closes
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任丽霞
于晓亮
袁晓燕
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Tianjin University
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Abstract

The present invention discloses the halogen of alkyl imidazole four and closes biphenyl type magnetic liquid crystal monomer of molysite substitution and preparation method thereof, with 5 ENBs 2,3 dicarboximides are raw material, biphenyl liquid crystal primitive and structural type magnetic primitive are incorporated into small molecule simultaneously, it is prepared for having concurrently the monomer of liquid crystal behavior and magnetic behavior, the application of such material is expanded, there is potential application preparing information storage material, absorbing material, magnetic imaging, electronical display etc..

Description

The halogen of alkyl imidazole four closes biphenyl type magnetic liquid crystal monomer and its preparation of molysite substitution Method
Technical field
The present invention relates to a kind of Polymerizable ionic liquid monomer, polymer and its synthesis side containing biphenyl liquid crystal primitive Method, more particularly, the preparation method of more particularly to a kind of small molecule magnetic ionic liquids containing biphenyl liquid crystal primitive and The side chain type molecule rank magnetic liquid crystal of a kind of structure-controllable is synthesized using the ring-opening metathesis polymerization of Grubbs three generations reagent catalysis The method of polymer.
Background technology
Magnetic functional material, it is a kind of ancient and widely used material.On this basis, magnetic polymer material, because The features such as its low-density, easy processing are molded, shape and size easy to control, and pliability is good, has bigger application prospect.Magnetic is high Molecule can be divided into compound magnetic macromolecule and structure type magnetic macromolecule materials according to its preparation method.Compound magnetic macromolecule is Referring to will be compound as the high polymer material of matrix and the progress of inorganic strong magnetic material, but there is magnetic-particle point for such a method Cloth is uneven, the problems such as Miscibility difference, limits the application of material.And structure type magnetic macromolecule materials then overcome kind Kind shortcoming, by the magnetic of polymer itself, realizes the integration of magnetic and polymer property.2004, Japanese Hyashi Made first with Hamaguchi professors (S.Hayashi et al., Chemistry Letters, 2004,33,1590-1591.) It is standby gone out organic magnetic ionic liquid --- four halogen close the quaternary ammonium alkyl ionic liquid of iron (III) acid ion.After tested, should Material has certain paramagnetism.2011, Hispanic Markus(the M. such as VaskoJovanovskiEt al., Polymer Chemistry, 2011,2,1275-1278.) magnetic ionic liquids primitive is introduced first To polymer lateral chain, it is prepared for that there is paramagnetic magnetic polymer.So far, magnetic ionic liquids have opened up structural type magnetic material The new branch of material.
Liquid crystal, refer to Cucumber in molten condition or after being dissolved by the solvent, although losing the rigidity of solid matter, obtain The easy mobility of liquid was obtained, and maintains the anisotropy ordered arrangement of partiallycrystalline states material molecule, one kind is formed and has crystalline substance concurrently The intermediate state of some properties of body and liquid.German physiologist R.C.Virchow has found the myelin material of nature first With liquid crystal characteristic.And to the formal research of liquid crystal, start from Austrian botanist F.Reinitzer in 1888 (F.Reinitzer.,Monatshefte für Chemie und verwandteTeileandererWissenschaften, 1888,9,421-441.) observation to benzoic acid cholesteryl ester.From the twenties in 19th century, with going deep into for research, liquid crystal Synthesis and classification are further perfect, G.Friedel (G.Friedel., Annales de Physique, 1922,18,162-174.) Liquid crystal is categorized into stratose type or away from row type (smectic type), nematic, cholesterol type (cholesteric).At present, liquid crystal material is extensive Applied to field of electronic display, because the advantages that driving voltage is low, power consumption is small, reliability is high, display information amount is big, receives The favor of people.It is not already very novel concept that liquid crystal unit, which is introduced in macromolecule,.T.Ichikawa(T.Ichikawa Et al., Journal of the American Chemical Society, 2012,134,11354-11357.) and J.Lim (J.Lim et al., International Journal ofPharmaceutics.2015,490,265-272.) is with regard to respectively It is applied to proton conduction and medicine controlled releasing, compared with general material, its performance has very big lifting.However, liquid crystal material With the combination of magnetic material, report is but had no.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of magnetic small molecular ion containing liquid crystal unit Liquid and preparation method thereof, and a kind of magnetic polymer and its synthetic method containing liquid crystal unit.
The technical purpose of the present invention is achieved by following technical proposals：
The halogen of alkyl imidazole four closes the biphenyl type magnetic liquid crystal monomer of molysite substitution, has following chemical structural formulas
The preparation method of above-mentioned ionic liquid, carry out as steps described below：
Step 1, by 5- ENBs -2,3- dicarboximide and Isosorbide-5-Nitrae-dibromobutane with mol ratio 1:The ratio of (1-10) Example, 20-25 degrees Celsius of room temperature is reacted under the conditions of existing for Anhydrous potassium carbonate, obtains intermediate product a, wherein middle produce Thing a chemical constitutions are as follows：
In step 1, by Isosorbide-5-Nitrae-dibromobutane and Anhydrous potassium carbonate it is dispersed after, be added to 5- ENBs -2,3- Reacted in the DMF solution of dicarboximide, the reaction time at least 12h, preferably 12-48h.
Step 2, intermediate product a step 1 obtained, reacted in the basic conditions with even phenol, both mol ratios For 1:(1-5), obtain intermediate product b；Intermediate product b chemical constitution is as follows：
In step 2, after intermediate product a being dispersed in into acetone, being added to dispersed has even phenol and hydroxide In the acetone of potassium, even the mol ratio of phenol and potassium hydroxide is 1：(1—2)；Reaction temperature is 30-80 DEG C, and preferably 50-70 take the photograph Family name's degree；Reaction time at least 12h, preferably 12-48h.
Step 3, intermediate product b and 1,10- dibromo-decane that step 2 obtains are reacted in the basic conditions, mole Than 1:(1-30), obtains intermediate product c, and intermediate product c chemical constitution is as follows：
In step 3, it is intermediate product b, 1,10- dibromo-decanes and the dispersed progress in acetone of potassium hydroxide is anti- Should, the mol ratio of intermediate product b and potassium hydroxide is 1：(1—2)；Reaction temperature is 30-80 DEG C, preferably 50-70 degrees Celsius； Reaction time at least 12h, preferably 12-48h.
Step 4, intermediate product c step 3 obtained carries out quaternary ammonium reaction with N- methylimidazoles, then carries out ion exchange So that chlorion carries out ion exchange with quaternary ammonium reaction product, the small molecular ion liquid d containing liquid crystal unit is obtained, containing liquid crystal The small molecular ion liquid d of primitive chemical constitution is as follows：
In step 4, intermediate product c and N- methylimidazole is dispersed in acetone, reaction temperature is 30-80 DEG C, It is preferred that 50-70 degrees Celsius；Reaction time at least 12h, preferably 12-48h.
In step 4, make it that intermediate product c is at utmost quaternary ammoniated, select N- methylimidazoles excessive, such as intermediate product C dosage (amount of material, mole mmol) is 1 with the dosage (volume ml) of N- methylimidazoles：(1—2).
In step 4, ion exchange resin used in ion exchange process is chlorion exchanger resin, is handed over using ion Change resin and chlorion is provided, ion-exchange reactions is carried out with intermediate product, reaction temperature is 20-25 degrees Celsius of room temperature, during reaction Between be 4-12h.
In step 4, to ensure ion-exchange effect, ion exchange resin addition needs excess, such as uses 5-10 quality The ion exchange resin of part, 1 mass parts are 1g.
Step 5, small molecular ion the liquid d and FeCl containing liquid crystal unit step 4 obtained4·H2O is reacted, and is obtained The biphenyl type magnetic ionic liquids A of molysite substitution, i.e., the magnetic small molecular ion liquid containing liquid crystal unit are closed to the halogen of alkyl imidazole four Body A, chemical constitution are as follows：
In steps of 5, by small molecular ion liquid d and FeCl containing liquid crystal unit4·H2O is dispersed to be entered in methyl alcohol Row reaction, both are equimolar ratio；Reaction temperature is 30-60 DEG C, preferably 40-55 degrees Celsius；At least 12 hours reaction time, It is preferred that 24-48 hours.
After completing often to walk preparation process, purification can be accomplished in several ways for product, for example, column chromatography, filtering, Extraction, rotary evaporation.
The halogen of alkyl imidazole four closes the biphenyl type magnetic function polymer of molysite substitution, has following chemical structural formulas
Polymerization degree n is 50-300.
Above-mentioned polymer is prepared as steps described below：Under the catalysis of Grubbs three generations reagent, made using intermediate product d For polymerized monomer, prepared by active ring-opening metathesis polymerization method, then again by polymer and FeCl4·H2O reaction, The biphenyl type magnetic function polymer that the halogen of alkyl imidazole four closes molysite substitution is obtained, wherein intermediate product d chemical structural formula is： That is applications of the intermediate product d in magnetic polymer is prepared.
In above-mentioned preparation method, Grubbs three generations reagent and intermediate product d mol ratio are 1：(50—300).
In above-mentioned preparation method, using the mixed solution of DMF and water as reaction dissolvent, uniformly Scattered intermediate product d；Using N, the dispersed Grubbs three generations reagent of N- dimethyl formyls.
In above-mentioned preparation method, in the mixed solution of DMF and water, DMF with The volume ratio of water is (1-5)：1.
In above-mentioned preparation method, by the DMF solution of Grubbs three generations's reagents, it is added to and uniformly divides Dissipate in intermediate product d DMF and the mixed solution of water, and polymerize under 20-25 degrees Celsius of room temperature Reaction.
In above-mentioned preparation method, during active ring-opening metathesis polymerization, polymerization reaction time at least 6 hours, to carry High conversion, can proper extension polymerization reaction time, such as 6-24h.
In above-mentioned preparation method, obtained polymer is pressed into repeat unit and FeCl4·H2O equimolar parts enter Row reaction, you can obtain the biphenyl type magnetic function polymer that the halogen of alkyl imidazole four closes molysite substitution；In the reaction, react molten Agent is methanol, and reaction temperature is 30-60 DEG C, preferably 40-55 degrees Celsius；In at least 12 hours reaction time, preferably 24-48 is small When.
In above-mentioned preparation method, during active ring-opening metathesis polymerization, using stirring so that system uniformly participates in instead Should.
In above-mentioned preparation method, terminator is added to terminate active ring opening metathesis polymerization.
In above-mentioned preparation method, the terminator is vinyl ethyl ether.
In above-mentioned preparation method, after terminating active ring opening metathesis polymerization, by reaction solution be added drop-wise in ether precipitation, Sediment is centrifuged to obtain, is finally dried.
In above-mentioned preparation method, add terminator and terminate in polymerization process, using stirring so that the equal right amount of system Only react, it is contemplated that the influence factor such as extent of reaction, at least 30min, preferably 0.5-1h are stirred after terminator is added, with end Only polymerisation.
In above-mentioned preparation method, active ring-opening metathesis polymerization is carried out using the catalysis of Grubbs three generations reagent, is entirely being lived In property polymerization process, to realize the controllable of the molecular structure of magnetic polymer, molecular weight and molecular weight distribution.
In above-mentioned preparation method, the coefficient of dispersion of the polymer molecular weight of preparation is less than 1.3.
In above-mentioned preparation method, the polymerization degree n of the polymer of preparation is 50-300.
In the polymer preparation process of the present invention, the catalyst used is Grubbs three generations reagent (i.e. Grubbs three generations Catalyst), its chemical structural formula is as follows：
The catalyst is obtained by Grubbs bis- generations catalyst modifications, by the polymerization for the cis Norbornene derivative that it is catalyzed It is the polymerization of activity, it has the advantages that reaction condition is gentle, reaction is efficiently quick.The polymer that the polymerization obtains has molecule Measure controllable, the characteristic of dispersiveness narrow (General Decentralized coefficient is less than 1.3).Therefore the open loop for taking Grubbs three generations reagent to be catalyzed is easy The method of position polymerization, can be achieved the control and regulation to the molecular weight and molecualr weight distribution of magnetic polymer.Wherein polymer end The phenyl ring Ph of base comes from the phenyl ring Ph in Grubbs three generations's reagents, and the group of another end group of polymer is then anti-from polymerization The terminator added at the end of answering, terminator used is vinyl ethyl ether, so another end group of polymer is the knot of ether Structure (bibliography Anita Leitgeb, Julia Wappel, Christian Slugovc, The ROMP toolbox (2010) 2927-2946 of upgraded, Polymer 51).
Compared with existing various types of materials, by biphenyl liquid crystal primitive and structural type magnetic primitive in technical scheme It is incorporated into simultaneously and in polymer molecule, is prepared for having liquid crystal behavior and the monomer and polymer of magnetic behavior concurrently, expands this The application of class material.Meanwhile polymerisation uses the ring-opening metathesis polymerization of Grubbs three generations reagent catalysis, makes polymer Compound with regular structure is controllable, has certain designability.Technical solution of the present invention provide it is new, feasible, efficiently, structure-controllable Magnetic liquid crystal polymer synthetic method, this method has that reaction condition is gentle, substrate universality is good, atom utilization is high Feature, there is potential application preparing information storage material, absorbing material, magnetic imaging, electronical display etc..
Brief description of the drawings
Fig. 1 be a in embodiment 1 nmr spectrum (1H-NMR,500Hz,CDCl3)。
Fig. 2 be b in embodiment 2 nmr spectrum (1H-NMR,500Hz,CDCl3)。
Fig. 3 be c in embodiment 3 nmr spectrum (1H-NMR,500Hz,CDCl3)。
Fig. 4 be c nmr spectrum in embodiment 3 partial enlargement (1H-NMR,500Hz,CDCl3)。
Fig. 5 be d in embodiment 4 nmr spectrum (1H-NMR,500Hz,DMSO-d6)。
Fig. 6 be polymer in embodiment 6 nmr spectrum (1H-NMR,500Hz,DMSO-d6)。
Fig. 7 is A and B Raman spectrogram.
Fig. 8 is petrographic microscope images of the A in liquid crystal temperature range.
Fig. 9 is petrographic microscope images of the B in liquid crystal temperature range.
Figure 10 is A M-H magnetization curves.
Figure 11 is M-H magnetization curve of the polymer in 300K.
Figure 12 is partial enlarged drawing of the polymer in 300K M-H magnetization curves.
Figure 13 is M-H magnetization curve of the polymer in 380K.
Figure 14 is partial enlarged drawing of the polymer in 380K M-H magnetization curves.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.In the following embodiments, nuclear magnetic resonance Spectrometer is VARIAN INOVA 500MHz spectrometers；Raman spectrum is Renishaw-inVia reflex；Polarisation Microscope (POM) is Nikon ECLIPSE LV100N POL；Superconductive quantum interference is Quantum Design VSM (superconducting quantum interference device, SQUID) magnetometer.Reaction process condition Middle normal temperature is 20-25 degrees Celsius；Under agitation, mixing speed is 100-150 turns/min；Rate of addition is at the uniform velocity to drip Add, control and be added dropwise to complete in 20-30min.
Embodiment 1
Intermediate product a synthesis, its chemical constitution are as follows：
(1) by Isosorbide-5-Nitrae-dibromobutane (13.2190g, 60mmol), Anhydrous potassium carbonate is added in 250mL round-bottomed flask, And add the stirring of polytetrafluoroethylene (PTFE) magneton.5- ENB -2,3- dicarboximides (1.6651g, 10mmol) are added to Wiring solution-forming A in 100mL DMF, and solution A is added drop-wise in Isosorbide-5-Nitrae-dibromobutane.It is added dropwise to complete, continues stirring reaction 48h, Make its reaction complete.
(2) after reaction terminates, gained mixed system is filtered, filtrate moves into 500mL separatory funnels, adds 150mL distillations Water, then with the extraction of 50mL dichloromethane three times, combined dichloromethane phase, add anhydrous magnesium sulfate and be dried overnight.To dry Complete liquid filtering, collects filtrate, and removes solvent on a rotary evaporator, obtains crude product.
(3) crude product is separated by column chromatography, and petrol ether/ethyl acetate mixed solvent collects production as eluent Thing, revolving remove solvent, after vacuum drying, obtain white needle-like crystals.Yield：80%.Fig. 1 is a nmr spectrum.1HNMR(500MHz,CDCl3) δ 6.12 (t, J=1.8Hz, 2H), 3.38 (ddd, J=14.1,7.0,4.8Hz, 6H), 3.29- 3.22(m,2H),1.84-1.71(m,3H),1.66-1.51(m,3H)。
Embodiment 2
Intermediate product b synthesis, its chemical constitution are as follows：
(1) phenol (4.7023g, 25mmol) will be connected, potassium hydroxide (6.9803g, 50mmol), be added to the double of 250mL In neck bottle, polytetrafluoroethylene (PTFE) magneton is added, 50mL acetone is then added into bottle, is heated to 80 DEG C, reacts 30min.By centre 30mL acetone wiring solution-forming B are added in product a (1.4909g, 5mmol), solution B is instilled in reaction bulb.It is added dropwise to complete, continues Stirring, 80 DEG C of reaction 20h, make its reaction complete.
(2) after reaction terminates, gained mixture is moved into 500mL separatory funnel, adds 100mL distilled water, and use salt Sour fully acidifying, then with the extraction of 50mL ethyl acetate three times, combined ethyl acetate phase, add anhydrous magnesium sulfate and be dried overnight. The liquid filtering finished will be dried, collect filtrate, and remove solvent on a rotary evaporator, obtain crude product.
(3) crude product is separated by column chromatography, and petrol ether/ethyl acetate mixed solvent collects production as eluent Thing, revolving remove solvent, after vacuum drying, obtain white solid.Yield：50%.Fig. 2 is b nmr spectrum.1H NMR (500MHz,CDCl3) δ=7.42 (ddd, J=9.5,5.8,2.4,4H), 6.95-6.85 (m, 4H), 6.11 (t, J=1.7, 2H), 3.97 (t, J=6.1,2H), 3.43 (t, J=7.2,2H), 3.40 (m, 2H), 3.26 (dd, J=2.8,1.5,2H), 1.79-1.71 (m, 3H), 1.70-1.62 (m, 2H), 1.55 (d, J=8.8,1H).
Embodiment 3
Intermediate product c synthesis, its chemical constitution are as follows：
(1) by intermediate product b (403.47mg, 1mmol), 1,10- dibromo-decane (6.062g, 20mmol), potassium hydroxide (57mg, 1mmol) is added in 100mL round-bottomed flask, and adds polytetrafluoroethylene (PTFE) magneton, and 20mL third is then added into bottle Ketone, 60 DEG C are heated to, react 20h.
(2) after reaction terminates, gained mixture is moved into 125mL separatory funnel, adds 35mL distilled water, and use 50mL Ethyl acetate extracts three times, combined ethyl acetate phase, adds anhydrous magnesium sulfate and is dried overnight.The liquid filtering finished will be dried, Filtrate is collected, and removes solvent on a rotary evaporator, obtains crude product.
(3) crude product is separated by column chromatography, and petrol ether/ethyl acetate collects product, revolving is removed as eluent Solvent is removed, after vacuum drying, obtains white solid.Yield：100%.Fig. 3 is c nmr spectrum, and Fig. 4 is chemistry in Fig. 3 The partial enlarged drawing of displacement 1-2.1H NMR (500MHz, CDCl3) δ=7.45 (d, J=8.6,4H), 6.93 (t, J=9.2, 4H), 6.11 (s, 2H), 3.98 (q, J=6.2,4H), 3.46-3.36 (m, 6H), 3.28-3.22 (m, 2H), 1.89-1.83 (m, 2H), 1.79 (dd, J=14.7,6.9,2H), 1.76-1.71 (m, 3H), 1.69-1.61 (m, 2H), 1.54 (d, J=8.7, 1H), 1.46 (ddd, J=18.4,10.8,4.9,4H), 1.34 (d, J=21.3,6H).
Embodiment 4
Intermediate product d synthesis, its chemical constitution are as follows：
(1) intermediate product c (155.66mg, 0,25mmol) is added in 50mL round-bottomed flasks, and adds acetone 20mL, Then the μ L of N- methylimidazoles 250 are added into reaction bulb, are heated to 80 DEG C, react 48h.After completion of the reaction, product is rotated dense Contracting, is then added dropwise in excess diethyl ether, 3 times repeatedly, after vacuum drying, obtains white solid product dropwise.Yield 100%.
(2) 5g chlorion exchanger resins, stirring at normal temperature reaction will in above-mentioned white solid DMF/ water mixed solutions, be added 12h.After completion of the reaction, filter, concentrate solution, be then added dropwise to the product after concentration in excess diethyl ether dropwise, 3 times repeatedly. After vacuum drying, white solid product is obtained.Yield 100%.Fig. 4 is d nmr spectrum.1H NMR(500MHz, DMSO-d6) δ 9.29 (s, 1H), 7.80 (s, 1H), 7.73 (s, 1H), 7.49 (d, J=8.7,4H), 6.94 (dd, J=8.7, 1.9,4H), 6.02 (s, 2H), 4.15 (t, J=7.2,2H), 3.95 (q, J=6.1,6H), 3.84 (s, 3H), 3.31 (s, 2H), 3.25 (t, J=7.0,2H), 3.22 (s, 2H), 1.77 (m, 2H), 1.72-1.66 (m, 2H), 1.60 (m, 2H), 1.55-1.45 (m,4H),1.39(m,2H),1.26(m,10H)。
Embodiment 5
The synthesis of magnetic small molecular ion liquid containing liquid crystal unit, its chemical constitution are as follows：
(1) intermediate product d (66mg, 0.1mmol) is added in 25mL round-bottomed flasks, adds 10mL methanol and be allowed to molten Solution, then with wait material amount FeCl4·H2O reacts, temperature 50 C, reacts 24h.
(2) after completion of the reaction, product is concentrated, and is added dropwise in excess diethyl ether precipitates dropwise, washed, repeatedly for three times, obtain To brown solid.Yield 100%.
Embodiment 6
The synthesis of QAS polymer containing liquid crystal unit, its chemical constitution are as follows：
(1) intermediate product d (66mg, 0.1mmol) is taken, (isometric ratio) is dissolved with the mixed solution of DMF and water, by system Sealing, and take out and rush nitrogen 3 times, the nitrogen environment of system is kept, (d is 300 with catalyst molar ratio by Grubbs three generations reagent: 1) after being dissolved with DMF, added by syringe into reaction system.Normal-temperature reaction 24h, add terminator vinyl ethyl ether and terminate In polymerization process, using stirring so that system uniformly stops reacting, 0.5h is stirred after terminator is added, to terminate polymerization Reaction.
(2) after completion of the reaction, product is instilled in excess diethyl ether dropwise, repeatedly for three times, after vacuum drying, reaches brown and consolidate Body product.Yield 100%.Fig. 5 be the polymer nmr spectrum (1H-NMR,500Hz,DMSO-d6)。1H NMR (500MHz,CDCl3)δ9.36(broad,1H),7.80(broad,1H),7.74(broad,1H),7.37(broad,4H), 6.86(broad,4H),5.27-5.15(broad,2H),4.13(broad,2H),3.84(broad,7H),3.30-2.99 (broad,6H),1.73(broad,4H),1.68-1.42(broad,6H),1.33(broad,2H),1.21(broad,10H)。
Embodiment 7
Magnetic polymer synthesis containing liquid crystal unit：Synthesis mode is similar to Example 5, adds FeCl4·H2O is with polymerizeing The amount of the material of thing repeat unit keeps equimolar, and polymer is washed into drying after reacting, saves other reactions steps.
Labeled as B, (i.e. the halogen of alkyl imidazole four closes molysite and substituted magnetic polymer containing liquid crystal unit prepared by embodiment 7 Biphenyl type magnetic function polymer), the magnetic small molecular ion liquid mark containing liquid crystal unit prepared by embodiment 5 is A (i.e. the halogen of alkyl imidazole four closes the biphenyl type magnetic ionic liquids that molysite substitutes).In the semiconductor laser that excitation wavelength is 785nm Device, which excites down, to be scanned, wave number 333cm-1There is obvious vibration peak in place, from FeCl4-The symmetrical of middle Cl-Fe-Cl shakes Dynamic, monomer A shows consistent vibration peak with polymer B, illustrates identical structure FeCl be present in both4-.Using with heat The petrographic microscope of platform is observed, since 20-25 degrees Celsius of room temperature, 1 DEG C/min of heating rate, as shown in figs. 8 and 9, In A, B liquid crystal section, the optical stripe of different-shape is can observe, Fig. 8 observed temperature is 30 DEG C；Fig. 9 observation temperature Spend for 114 DEG C.Tested using SQUID, under conditions of 300K temperature, by applying -10000~10000Oe magnetic field, The corresponding intensity of magnetization is measured, as shown in Figure 10, for monomer A, there is obvious hysteresis curve, is illustrated for ferromagnetic material, Loop line claims coercivity H, size 150Oe with x-axis intersection point；Loop line claims remanence rate Mr, size 0.005emu/g with y-axis intersection point. Tested using SQUID, respectively under conditions of 300K and 380K temperature, by applying -10000~10000Oe magnetic field, The corresponding intensity of magnetization is measured, as shown in accompanying drawing 11-14, for polymer B, there is obvious hysteresis curve, explanation in 300K For ferromagnetic material, coercivity H size 11Oe；Remanence rate Mr, size 10.31 × 10-4emu/g；Temperature is lifted to 380K When, coercivity H, size 25Oe；Remanence rate Mr, size 34.52 × 10-4emu/g.With the rise of temperature, coercivity and surplus Residual magnetism rate has rise, shows as the rise of temperature, ferromagnetic property is remarkably reinforced, and this is different from the magnetic property of routine 's.Under the conditions of same test, the magnetic property of temperature test monomer is lifted, monomer A is showed from ferromagnetic property to paramagnetism Fundamental change, the magnetic property with routine is identical.
The adjustment that preparation technology is carried out according to the content of the invention prepares monomer A and polymer B, and is characterized, show with Basically identical property (the i.e. FeCl of above-described embodiment4-Middle Cl-Fe-Cl symmetric vibration and the optical stripe in liquid crystal section). Understood for monomer A magnetic characterization, at 300k, monomer A is ferromagnetic material, coercivity 148-155Oe of average out to, is remained Residual magnetism rate 0.0045-0.0055emu/g of average out to, raise and occur from ferromagnetic property to paramagnetism fundamental change with temperature；Pin The magnetic characterization of polymer B is understood, at 300k, polymer B is ferromagnetic material, 10-13Oe of coercivity average out to；It is surplus Residual magnetism rate average out to 10-10.5 × 10-4Emu/g, with temperature rise ferromagnetic property enhancing.It is prepared by monomer A and polymer B Application in information storage material, absorbing material, magnetic imaging field or field of electronic display.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal Fall into protection scope of the present invention.

Claims (10)

1. the halogen of alkyl imidazole four closes the biphenyl type magnetic liquid crystal monomer of molysite substitution, it is characterised in that has following chemical constitutions Formula
2. the halogen of alkyl imidazole four according to claim 1 closes the biphenyl type magnetic liquid crystal monomer of molysite substitution, its feature exists In at 300k, the biphenyl type magnetic ionic liquids that the halogen of alkyl imidazole four closes molysite substitution are ferromagnetic material, and coercivity is average For 148-155Oe, remanence rate 0.0045-0.0055emu/g of average out to, raise and occur from ferromagnetic property to suitable with temperature Magnetic fundamental change.
3. the halogen of alkyl imidazole four closes the preparation method of the biphenyl type magnetic liquid crystal monomer of molysite substitution, it is characterised in that under State step progress：
Step 1, by 5- ENBs -2,3- dicarboximide and Isosorbide-5-Nitrae-dibromobutane with mol ratio 1:The ratio of (1-10), 20-25 degrees Celsius of room temperature is reacted under the conditions of Anhydrous potassium carbonate is existing, obtains intermediate product a, wherein intermediate product aization It is as follows to learn structure：
Step 2, intermediate product a step 1 obtained, reacted in the basic conditions with even phenol, both mol ratios are 1: (1-5), obtain intermediate product b；Intermediate product b chemical constitution is as follows：
Step 3, intermediate product b and 1,10- dibromo-decane that step 2 obtains are reacted in the basic conditions, mol ratio 1: (1-30), obtains intermediate product c, and intermediate product c chemical constitution is as follows：
Step 4, the intermediate product c that step 3 is obtained carries out quaternary ammonium reaction with N- methylimidazoles, then carry out ion exchange so that Chlorion carries out ion exchange with quaternary ammonium reaction product, the small molecular ion liquid d containing liquid crystal unit is obtained, containing liquid crystal unit Small molecular ion liquid d chemical constitution it is as follows：
Step 5, small molecular ion the liquid d and FeCl containing liquid crystal unit step 4 obtained4·H2O is reacted, and obtains alkane The halogen of base imidazoles four closes the biphenyl type magnetic ionic liquids of molysite substitution, and chemical constitution is as follows：
4. the halogen of alkyl imidazole four according to claim 3 closes the preparation side of the biphenyl type magnetic liquid crystal monomer of molysite substitution Method, it is characterised in that in step 1, by Isosorbide-5-Nitrae-dibromobutane and Anhydrous potassium carbonate it is dispersed after, be added to 5- norborneols Reacted in the DMF solution of alkene -2,3- dicarboximide, the reaction time at least 12h, preferably 12-48h.
5. the halogen of alkyl imidazole four according to claim 3 closes the preparation side of the biphenyl type magnetic liquid crystal monomer of molysite substitution Method, it is characterised in that in step 2, after intermediate product a is dispersed in into acetone, be added to it is dispersed have even phenol and In the acetone of potassium hydroxide, even the mol ratio of phenol and potassium hydroxide is 1：(1—2)；Reaction temperature is 30-80 DEG C, preferably 50-70 degrees Celsius；Reaction time at least 12h, preferably 12-48h.
6. the halogen of alkyl imidazole four according to claim 3 closes the preparation side of the biphenyl type magnetic liquid crystal monomer of molysite substitution Method, it is characterised in that in step 3, by intermediate product b, 1,10- dibromo-decanes and potassium hydroxide is dispersed enters in acetone The mol ratio of row reaction, intermediate product b and potassium hydroxide is 1：(1—2)；Reaction temperature is 30-80 DEG C, and preferably 50-70 is Celsius Degree；Reaction time at least 12h, preferably 12-48h.
7. the halogen of alkyl imidazole four according to claim 3 closes the preparation side of the biphenyl type magnetic liquid crystal monomer of molysite substitution Method, it is characterised in that in steps of 5, by small molecular ion liquid d and FeCl containing liquid crystal unit4·H2O is dispersed in first Reacted in alcohol, both are equimolar ratio；Reaction temperature is 30-60 DEG C, preferably 40-55 degrees Celsius；Reaction time at least 12 Hour, preferably 24-48 hours.
8. the halogen of alkyl imidazole four according to claim 3 closes the preparation side of the biphenyl type magnetic liquid crystal monomer of molysite substitution Method, it is characterised in that in step 4, intermediate product c and N- methylimidazole is dispersed in acetone, reaction temperature 30- 80 DEG C, preferably 50-70 degrees Celsius；Reaction time at least 12h, preferably 12-48h；In step 4, to cause intermediate product c most Big degree is quaternary ammoniated, selects N- methylimidazoles excessive, such as intermediate product c dosage (amount of material, mole mmol) and N- methyl The dosage (volume ml) of imidazoles is 1：(1—2)；In step 4, ion exchange resin used in ion exchange process be chlorine from Sub-exchange resin, chlorion is provided using ion exchange resin, carries out ion-exchange reactions with intermediate product, reaction temperature is room 20-25 degrees Celsius of temperature, reaction time 4-12h；In step 4, to ensure ion-exchange effect, ion exchange resin adds Amount needs excess, such as uses the ion exchange resin of 5-10 mass parts, 1 mass parts are 1g.
9. the biphenyl type magnetic liquid crystal monomer that the halogen of alkyl imidazole four as claimed in claim 1 closes molysite substitution is deposited in preparation information Store up the application in material, absorbing material, magnetic imaging field or field of electronic display.
10. application of the small molecular ion liquid in magnetic polymer is prepared containing liquid crystal unit as shown in following chemical formula.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752278A (en) * 2018-06-27 2018-11-06 吉林化工学院 Imidazolium compounds and preparation method thereof of the one kind containing biphenyl group
CN110857282A (en) * 2018-08-24 2020-03-03 天津大学 Tetrahalomalysite-substituted dodecyl quaternary ammonium salt magnetic ionic liquid, polyionic liquid and self-assembly of polyionic liquid
CN110885324A (en) * 2018-09-10 2020-03-17 天津大学 Imidazole ionic salt with photo-magnetic dual response, preparation method thereof and detection of ferric ions in aqueous solution
CN112239516A (en) * 2019-07-16 2021-01-19 天津大学 Imidazole magnetic polymer containing alkyl chain, preparation method thereof and application thereof in electromagnetic materials

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992309A (en) * 2014-05-30 2014-08-20 天津大学 Side chain type magnetic monomer and polymer and controllable synthesis method thereof
CN104003926A (en) * 2014-05-30 2014-08-27 天津大学 Alkyl ammonium salt-based side chain type magnetic monomer and polymer as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992309A (en) * 2014-05-30 2014-08-20 天津大学 Side chain type magnetic monomer and polymer and controllable synthesis method thereof
CN104003926A (en) * 2014-05-30 2014-08-27 天津大学 Alkyl ammonium salt-based side chain type magnetic monomer and polymer as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIXIA REN, ET AL.: "Cobaltocenium-Containing Block Copolymers: Ring-Opening Metathesis Polymerization, Self-Assembly and Precursors for Template Synthesis of Inorganic Nanoparticles", 《MACROMOL. RAPID COMMUN.》 *
MARKUS DÖBBELIN, ET AL.: "Synthesis of paramagnetic polymers using ionic liquid chemistry", 《POLYM. CHEM.》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752278A (en) * 2018-06-27 2018-11-06 吉林化工学院 Imidazolium compounds and preparation method thereof of the one kind containing biphenyl group
CN110857282A (en) * 2018-08-24 2020-03-03 天津大学 Tetrahalomalysite-substituted dodecyl quaternary ammonium salt magnetic ionic liquid, polyionic liquid and self-assembly of polyionic liquid
CN110885324A (en) * 2018-09-10 2020-03-17 天津大学 Imidazole ionic salt with photo-magnetic dual response, preparation method thereof and detection of ferric ions in aqueous solution
CN110885324B (en) * 2018-09-10 2022-03-01 天津大学 Imidazole ionic salt with photo-magnetic dual response, preparation method thereof and detection of ferric ions in aqueous solution
CN112239516A (en) * 2019-07-16 2021-01-19 天津大学 Imidazole magnetic polymer containing alkyl chain, preparation method thereof and application thereof in electromagnetic materials
CN112239516B (en) * 2019-07-16 2022-03-01 天津大学 Imidazole magnetic polymer containing alkyl chain, preparation method thereof and application thereof in electromagnetic materials

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