CN104003926B - Based on the side chain type magnetic monomer of alkylammonium salt, polymer and its preparation method and application - Google Patents
Based on the side chain type magnetic monomer of alkylammonium salt, polymer and its preparation method and application Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 125000005210 alkyl ammonium group Chemical group 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 title abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 10
- 150000005309 metal halides Chemical class 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000013067 intermediate product Substances 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 15
- 229940006460 bromide ion Drugs 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 238000005342 ion exchange Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 150000008282 halocarbons Chemical class 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 claims description 7
- 229910003317 GdCl3 Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- -1 12-(dimethylamino) dodecyl Chemical group 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical group CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 4
- HVOBSBRYQIYZNY-UHFFFAOYSA-N 2-[2-(2-aminoethylamino)ethylamino]ethanol Chemical compound NCCNCCNCCO HVOBSBRYQIYZNY-UHFFFAOYSA-N 0.000 claims description 3
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 claims description 3
- ZUXUNWLVIWKEHB-UHFFFAOYSA-N n',n'-dimethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN ZUXUNWLVIWKEHB-UHFFFAOYSA-N 0.000 claims description 3
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000011358 absorbing material Substances 0.000 abstract description 3
- 238000003384 imaging method Methods 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 17
- 238000001069 Raman spectroscopy Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical class C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- Chemical & Material Sciences (AREA)
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- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Hard Magnetic Materials (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
Disclosure is based on the side chain type magnetic monomer of alkylammonium salt, polymer and its preparation method and application, by cis 5 norborene after quaterisation outer 2,3 dicarboxylic anhydrides and metal halide react prepares the magnetic monomer of tool, and make that monomer has the unit that can participate in polyreaction, then, under Grubbs three generations's reagent catalysis, the magnetic monomer of synthesis prepares the magnetic polymer of structure-controllable by activity ring-opening metathesis polymerization method. Technical solution of the present invention provides the synthetic method of the magnetic polymer of a kind of structure-controllable, the method have easy and simple to handle, reaction condition is gentle, has potential application in preparing information storage material, absorbing material, magnetic imaging etc.
Description
Technical field
The present invention relates to a class magnetic polymerisable monomer, polymer and synthetic method thereof, more particularly, the controlled side chain type molecule rank magnetic polymer of a class formation and synthetic method thereof are synthesized particularly to the ring-opening metathesis polymerization utilizing Grubbs three generations's reagent catalysis.
Background technology
Magnetic polymer material is compared with conventional inorganic magnetic material, have that density is low, light weight, flexibility, easy machine-shaping, molecular structure are easy to design, are prone to the advantages such as functionalization, have wide practical use in information storage material, Magneto separate, absorbing material, magnetic imaging and drug controlled release etc. The preparation method of magnetic polymer material is broadly divided into two kinds according to its structure. One class is composite algorithm, it is doped in polymeric matrix by inorganic magnetic granule, but magnetic high-molecular existing defects prepared by this method, magnetic-particle skewness and the poor compatibility with Polymer Systems, doping is restricted, its magnetic derives from the inorganic particle of doping rather than polymer itself, belongs to the magnetic material of hydridization; Another kind of is chemical method, and the magnetic of the structure type magnetic macromolecule materials of this type of method synthesis derives from certain part of polymer itself or polymer composition, is the other magnetic high-molecular of molecular level. But polymer prepared by this type of method has big conjugated structure, exist cost of material height, complicated process of preparation, synthesis polymer solubility difference etc. shortcoming.
2004, Hyashi and the Hamaguchi of Japan taught a kind of little molecule of novel magnetic ionic liquids of (S.Hayashietal., ChemistryLetters, 2004,33,1590-1591.) reported first. This ionic liquid is made up of with the metal halogen compound anion containing high-spin metal center quaternary ammonium cation; 2011, HispanicDeng (M.Etal., PolymerChemistry, 2011,2,1275-1278.) reported first closes the preparation of the poly ion liquid of liron anions containing four halogen, by post-decoration method, polyimidazole is carried out ion exchange, close liron anion with four halogen and replace original anion, thus preparing magnetic polymer. The little molecule of magnetic ionic liquids of the report such as Hyashi and Hamaguchi does not possess the advantage of macromolecule polyalcohol, as good processing characteristics, molecular structure are easy to design, are prone to functionalization etc. Due to post-decoration method not up to 100% conversion ratio, thereforeDeposit defect structurally in the polymer prepared, the performance of magnetic polymer is also had corresponding impact.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of magnetic monomer.
The present invention also aims to the preparation method that a kind of magnetic monomer is provided.
A kind of magnetic polymer of offer is provided.
Further object is that the synthetic method that magnetic polymer is provided.
Further object is that the application that magnetic polymer is provided.
The above-mentioned purpose of the present invention is achieved by following technical proposals:
Based on the side chain type magnetic monomer of alkylammonium salt, there is the structure of chemical structure of general formula (I):
A+For-(CH2CH2)nN+(CH3)3, n=1,2,3,6;-CH2CH2N+(CH3)2CH2CH2N+(CH3)2CH2CH2OH, B-For FeCl4 -、FeCl3Br-、GdCl3Br-、GdCl4 -。
The preparation method of magnetic monomer, selects outer 2,3 dicarboxylic anhydrides of cis 5 norborene as raw material, and as shown in chemical structure of general formula (II), raw material is purchased from Sigma-aldrich, purity 95%, and No. ACS is 2746-19-2; Specifically, carry out as steps described below:
Outer for cis 5 norborene 2,3 dicarboxylic anhydrides and amine micromolecular are obtained by reacting the first intermediate product according to equimolar ratio example by step 1;
Step 2, the first intermediate product step 1 obtained and halogenated hydrocarbons carry out quaterisation and obtain the second intermediate product;
Step 3, the second intermediate product step 2 obtained and ion exchange resin carry out ion exchange, obtain the 3rd intermediate product;
Step 4, the 3rd intermediate product step 3 obtained and metal halide obtain magnetic monomer after reacting.
In described step 1, described amine micromolecular is N, N-dimethyl-ethylenediamine, 4-dimethylaminobutylamine, 6-(dimethylamino) hexylamine, 12-(dimethylamino) dodecyl amine, or 2-[[2-[(2-amino-ethyl) amino] ethyl] amino] ethanol.
In described step 1, outer 2,3 dicarboxylic anhydrides of described cis 5 norborene and the micromolecular consumption of amine are equimolar ratio.
In described step 1, utilize dichloromethane for reaction dissolvent, be sufficiently stirred for cis 5 norborene outer 2,3 dicarboxylic anhydrides, amine micromolecular and dichloromethane are uniform to realize system, reacting cmpletely at 120～130 DEG C, the response time is 4h at least, it is preferable that 4 8h.
In described step 2, described halogenated hydrocarbons is iodomethane.
In described step 2, for guaranteeing the first intermediate product extent of reaction in quaternization, described halogenated hydrocarbons is excessive, and its consumption is (1 5) with the mol ratio of 2,3 dicarboxylic anhydrides outside cis 5 norborene: 1.
In described step 2, utilize oxolane for reaction dissolvent, dissolve the first intermediate product and add halogenated hydrocarbons and react, for guaranteeing the first intermediate product extent of reaction in quaternization, it is preferable that 25～70 DEG C of reaction 2～12h.
In described step 3, described ion exchange resin is chloride ion exchanger resin, bromide ion exchanger resin, utilizes ion exchange resin to provide chloride ion, bromide ion, carries out ion-exchange reactions with the second intermediate product.
In described step 3, utilize absolute methanol for reaction dissolvent, dissolve the second intermediate product and add ion exchange resin and carry out ion-exchange reactions, consider exchange capacity and the ion-exchange effect of actually used ion exchange resin, select reaction system is stirred, the at least 4 hours response time at room temperature 20 25 DEG C, it is preferable that 6 10 hours.
In described step 4, described metal halide is ferric chloride, Iron(III) chloride hexahydrate, gadolinium trichloride or six trichloride hydrate gadoliniums.
In described step 4, the consumption of described metal halide and the 3rd intermediate product is equimolar ratio.
In described step 4, utilize absolute methanol for reaction dissolvent, dissolve the 3rd intermediate product and add metal halide and react, it is considered to the degree of reaction and process, for guaranteeing reaction conversion ratio and degree, react 8～12h room temperature 20 25 DEG C.
In above-mentioned preparation process, select to use filtration, rotary evaporation and dry method to purify, to respectively obtain the first intermediate product, the second intermediate product, the 3rd intermediate product and final magnetic monomer.
Magnetic polymer, has the polymer of following chemical structure of general formula (III):
A+For-(CH2CH2)nN+(CH3)3, n=1,2,3,6;-CH2CH2N+(CH3)2CH2CH2N+(CH3)2CH2CH2OH, B-For FeCl4 -、FeCl3Br-、GdCl3Br-、GdCl4 -, Ph is phenyl ring.
The preparation method of magnetic polymer, under Grubbs three generations's reagent catalysis, is utilized the magnetic monomer with chemical structure of general formula (I) structure as polymerization single polymerization monomer, is prepared by activity ring-opening metathesis polymerization method:
A+For-(CH2CH2)nN+(CH3)3, n=1,2,3,6;-CH2CH2N+(CH3)2CH2CH2N+(CH3)2CH2CH2OH, B-For FeCl4 -、FeCl3Br-、GdCl3Br-、GdCl4 -。
In above-mentioned preparation method, the mol ratio of Grubbs three generations's reagent and magnetic monomer is 1:(100 300).
In above-mentioned preparation method, adopt DMF as reaction dissolvent, dissolve Grubbs three generations's reagent and magnetic monomer respectively.
In above-mentioned preparation method, the DMF dissolving magnetic monomer is joined in the DMF dissolving Grubbs three generations's reagent, at room temperature 20 25 DEG C, carries out polyreaction.
In above-mentioned preparation method, in activity ring-opening metathesis polymerization process, utilize stirring so that system uniformly participates in reaction.
In above-mentioned preparation method, in activity ring-opening metathesis polymerization process, polymerization reaction time is 10 30min, for further fully reaction and/or improve conversion ratio, can proper extension polymerization reaction time on 0.5 hour, it is preferable that 1 6h.
In above-mentioned preparation method, add terminator to terminate activity ring opening metathesis polymerization.
In above-mentioned preparation method, described terminator is vinyl ethyl ether.
In above-mentioned preparation method, add terminator and terminate in polymerization process, utilize stirring so that the uniform stopped reaction of system, it is contemplated that the influence factors such as the extent of reaction, after adding terminator, stir at least 30min, it is preferable that 0.5 1h, to terminate polyreaction.
In above-mentioned preparation method, terminate activity ring opening metathesis polymerization after, reactant liquor is added drop-wise in dichloromethane completely precipitation, centrifugation obtain precipitate, in dichloromethane by polymer precipitate, drying to obtain magnetic polymer.
In above-mentioned preparation method, Grubbs three generations's reagent catalysis is utilized to carry out activity ring-opening metathesis polymerization, in whole living polymerization process, to realize the controlled 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 60 180.
In the polymer preparation process of the present invention, the catalyst of use is Grubbs three generations's reagent (i.e. Grubbs three generations catalyst), has the structure of chemical structure of general formula (IV):
By the polymerization that the polymerization of the cis Norbornene derivative of its catalysis is activity, it has reaction condition gentleness, the reaction advantage such as efficiently quick. It is controlled that the polymer that this polymerization obtains has molecular weight, the characteristic of dispersibility narrow (General Decentralized coefficient is less than 1.3). Therefore the method taking the ring-opening metathesis polymerization of Grubbs three generations's reagent catalysis, it may be achieved control and the adjustment to the molecular weight and molecualr weight distribution of magnetic polymer. Wherein the phenyl ring Ph of polymer terminal group comes from the phenyl ring Ph in Grubbs three generations's reagent, the group of another end group of polymer then derives from the terminator added when polyreaction terminates, terminator used is vinyl ethyl ether, so another end group of polymer is structure (the list of references AnitaLeitgeb of ether, JuliaWappel, ChristianSlugovc, TheROMPtoolboxupgraded, Polymer51 (2010) 2,927 2946).
Compared with prior art, monomer after quaterisation and metal halide are reacted by technical scheme and prepares the magnetic monomer of tool, and make that monomer has the unit that can participate in polyreaction, namely the polymerisable monomer containing be magnetic primitive and perfect structure is synthesized, then, under Grubbs three generations's reagent catalysis, the magnetic monomer of synthesis prepares the magnetic polymer of structure-controllable by activity ring-opening metathesis polymerization method. Technical solution of the present invention provide a kind of novel, feasible, efficiently, the synthetic method of the magnetic polymer of structure-controllable, the method has feature easy and simple to handle, that reaction condition is gentle, substrate universality is good, atom utilization is high, and magnetic polymer has potential application in preparing information storage material, absorbing material, magnetic imaging and drug controlled release etc.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the magnetic monomer of preparation in the embodiment of the present invention 1.
Fig. 2 is the mass spectrogram of the magnetic monomer of preparation in the embodiment of the present invention 1.
Fig. 3 is that polymer prepared by the present invention is attracted, by neodium magnet, the process schematic of getting up.
Fig. 4 is the NMR spectra of the polymer utilizing technical solution of the present invention to prepare.
Fig. 5 is the superconductive quantum interference figure of the polymer utilizing the magnetic monomer of the embodiment of the present invention 1 to prepare.
Fig. 6 is the superconductive quantum interference figure of the polymer utilizing the magnetic monomer of the embodiment of the present invention 10 to prepare.
Fig. 7 is the superconductive quantum interference figure of the polymer utilizing the magnetic monomer of the embodiment of the present invention 13 to prepare.
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with specific embodiment.
Raw material form is as follows:
Instrument form is as follows:
All the other reagent and raw material are purchased from the double; two ship chemical reagent factory in Tianjin, and the room temperature in preparation process is 20 25 DEG C.
Embodiment 1
Synthesize the magnetic monomer of structure shown in following chemical formula:
(1) by cis-5-norborene-outer-2,3-dicarboxylic anhydride (864.1mg, 5.0mmol) it is dissolved in the 10mL dichloromethane dried, add N, N-dimethyl-ethylenediamine (0.6mL, 5.0mmol), stirs 4～24h, being warming up to 120～130 DEG C of complete reaction 4h and dry to obtain intermediate product 1a, period utilizes Rotary Evaporators to remove dichloromethane in reaction system;
(2) being dissolved in 10mL oxolane by 1a (222.4mg, 1.0mmol), at addition iodomethane (0.3mL, 4.8mmol) room temperature 25 DEG C, there is precipitation in stirring 2h, dries to obtain intermediate product 1b after oxolane washs;
(3) 1b (896.1mg, 3.2mmol) is dissolved in 300mL absolute methanol, in system, adds 5g chloride ion exchanger resin stirring reaction 4h, dry after filtration, Rotary Evaporators remove solvent and to obtain intermediate product 1c;
(4) by 1c (732.2mg, 2.0mmol) it is dissolved in 150mL absolute methanol, Iron(III) chloride hexahydrate (531.6mg is added in system, 2.0mmol) the rotated evaporimeter of stirring reaction 8～12h dries to obtain solid magnetic monomer 1 after removing solvent, through Raman and mass spectral analysis it can be seen that 337cm in Raman collection of illustrative plates-1Place is the absworption peak of Fe-Cl; Theoretical molecular quasi-molecular ions m/z is 249.2, actual is measured as 249.1.
Embodiment 2
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 1, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, can obtain solid magnetic monomer 2. In Raman collection of illustrative plates 334,349,400cm-1Place is the absworption peak of Fe-Cl, 224,245,273cm-1Place is the absworption peak of Fe-Br; Theoretical molecular quasi-molecular ions m/z is 249.2, actual is measured as 249.1.
Embodiment 3
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 1, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, and the Iron(III) chloride hexahydrate used by step (4) changes six trichloride hydrate gadoliniums into, obtains solid magnetic monomer 3. Theoretical molecular quasi-molecular ions m/z is 249.2, actual is measured as 249.1.
Embodiment 4
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 1, N, N-dimethyl-ethylenediamine used changes 4-dimethylaminobutylamine into, and step (2) room temperature reaction 2h changes 70 DEG C of back flow reaction 12h into, obtains solid magnetic monomer 4. 337cm in Raman collection of illustrative plates-1Place is the absworption peak of Fe-Cl; Theoretical molecular quasi-molecular ions m/z is 277.2, actual is measured as 277.1.
Embodiment 5
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 4, chloride ion exchanger resin used changes bromide ion exchanger resin into, obtains solid magnetic monomer 5. In Raman collection of illustrative plates 334,349,400cm-1Place is the absworption peak of Fe-Cl, 224,245,273cm-1Place is the absworption peak of Fe-Br; Theoretical molecular quasi-molecular ions m/z is 277.2, actual is measured as 277.1.
Embodiment 6
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 4, chloride ion exchanger resin used changes bromide ion exchanger resin into, and Iron(III) chloride hexahydrate used changes six trichloride hydrate gadoliniums into, obtains solid magnetic monomer 6. Theoretical molecular quasi-molecular ions m/z is 277.2, actual is measured as 277.1.
Embodiment 7
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the preparation method of embodiment 1, N used by step (1), N-dimethyl-ethylenediamine changes 6-(dimethylamino) hexylamine into, and step (2) room temperature reaction 2h changes 70 DEG C of back flow reaction 12h into, obtains solid magnetic monomer 7. 337cm in Raman collection of illustrative plates-1Place is the absworption peak of Fe-Cl; Theoretical molecular quasi-molecular ions m/z is 305.2, actual is measured as 305.1.
Embodiment 8
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 7, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, obtains solid magnetic monomer 8. In Raman collection of illustrative plates 334,349,400cm-1Place is the absworption peak of Fe-Cl, 224,245,273cm-1Place is the absworption peak of Fe-Br; Theoretical molecular quasi-molecular ions m/z is 305.2, actual is measured as 305.1.
Embodiment 9
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 7, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, and the Iron(III) chloride hexahydrate used by step (4) changes six trichloride hydrate gadoliniums into, obtains solid magnetic monomer 9. Theoretical molecular quasi-molecular ions m/z is 305.2, actual is measured as 305.1.
Embodiment 10
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 1, N used by step (1), N-dimethyl-ethylenediamine changes 2-[[2-[(2-amino-ethyl) amino] ethyl] amino] ethanol into, step (2) room temperature reaction 2h changes 70 DEG C of back flow reaction 12h into, obtains solid magnetic monomer 10. 337cm in Raman collection of illustrative plates-1Place is the absworption peak of Fe-Cl; Theoretical molecular quasi-molecular ions m/z is 351.3, actual is measured as 351.2.
Embodiment 11
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 10, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, obtains solid magnetic monomer 11. In Raman collection of illustrative plates 334,349,400cm-1Place is the absworption peak of Fe-Cl, 224,245,273cm-1Place is the absworption peak of Fe-Br; Theoretical molecular quasi-molecular ions m/z is 351.3, actual is measured as 351.2.
Embodiment 12
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 10, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, and the Iron(III) chloride hexahydrate used by step (4) changes six trichloride hydrate gadoliniums into, obtains solid magnetic monomer 12. Theoretical molecular quasi-molecular ions m/z is 351.3, actual is measured as 351.2.
Embodiment 13
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 1, in the N used by step (1), N-dimethyl-ethylenediamine changes 12-(dimethylamino) dodecyl amine into, and step (2) room temperature reaction 2h changes 70 DEG C of back flow reaction 12h into, obtains solid magnetic monomer 13;337cm in Raman collection of illustrative plates-1Place is the absworption peak of Fe-Cl; Theoretical molecular quasi-molecular ions m/z is 389.3, actual is measured as 389.2.
Embodiment 14
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 13, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, obtains solid magnetic monomer 14. In Raman collection of illustrative plates 334,349,400cm-1Place is the absworption peak of Fe-Cl, 224,245,273cm-1Place is the absworption peak of Fe-Br; Theoretical molecular quasi-molecular ions m/z is 389.3, actual is measured as 389.2.
Embodiment 15
Synthesize the magnetic monomer of structure shown in following chemical formula:
Basically identical with the method for embodiment 13, the chloride ion exchanger resin used by step (3) changes bromide ion exchanger resin into, and the Iron(III) chloride hexahydrate used by step (4) changes six trichloride hydrate gadoliniums into, obtains solid magnetic monomer 15. Theoretical molecular quasi-molecular ions m/z is 389.3, actual is measured as 389.2.
The preparation of embodiment 16 magnetic polymer, the magnetic monomer selecting above-described embodiment to prepare respectively, utilize Grubbs three generations's catalyst to carry out activity ring-opening metathesis polymerization
By Grubbs three generations's catalyst, magnetic monomer 1:(100～300 in molar ratio) it is dissolved in N respectively, in dinethylformamide, monomer is joined in catalyst solution, reaction 10～30min is stirred at room temperature be polymerized, reaction adds 0.5mL vinyl ethyl ether stirring 30min and terminates reaction after terminating, reactant liquor is added drop-wise in dichloromethane and precipitates completely, centrifugation obtains precipitate, with dichloromethane, polymer is precipitated three times, dry to obtain target product magnetic polymer, apparent have the polymer of 2 C for A+ and show as yellow solid powder, all the other polymer are the solid that rufous is membranaceous. reaction equation is as follows:
Owing to the polymer belt of preparation is magnetic, for carrying out nuclear magnetic resonance, NMR test, first polymer and ion exchange resin are carried out abundant exchange reaction, with by metal ion exchanged for chloride ion or bromide ion, again polymer is carried out NMR test, the NMR test of all polymer all proves the basic structure of the polymer of each different side chains, and in the process of ion exchange, polymer architecture does not produce fundamental change. For following A+For-CH2CH2N+(CH3)3, B-For FeCl4 -The polymer of group is example, carries out brief analysis as follows, as shown in Figure 4:1HNMR(500Hz,DMSO-d6) chemical shift δ: a (bimodal, broad peak, main chain CHCH), e, f (broad peak, side chain O=CNCH2CH2N+(CH3)3), b, d (broad peak, CHCH2CHCHCHC=O), g (broad peak, side chain N+(CH3)3), c (bimodal, broad peak, main chain CHCH2CH), c'(is bimodal, broad peak, main chain CHCH2CH)。
Above-mentioned polymer prepared by the present invention is attracted, by neodium magnet, the process schematic of getting up, as shown in Figure 3. The magnetic polymer of preparation is carried out superconductive quantum interference, to characterize its magnetic behavior, the magnetic behavior that the performance of each magnetic polymer is essentially identical, prepares polymer for the magnetic monomer of embodiment 1,10,13 and carries out magnetism testing, and result is such as shown in attached Figure 57.
In the embodiment of above-mentioned preparation, can passing through to adjust reaction temperature, time and raw material type, ratio etc. be prepared, end product (no matter magnetic monomer or magnetic polymer) all shows the character essentially identical with above-described embodiment.
Above the present invention has been done exemplary description; should be noted that; when without departing from the core of the present invention, any simple deformation, amendment or other those skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.
Claims (8)
1. based on the side chain type magnetic monomer of alkylammonium salt, it is characterised in that have the structure of chemical structure of general formula (I):
Wherein A+For-(CH2CH2)nN+(CH3)3, n=1,2,3,6;-CH2CH2N+(CH3)2CH2CH2N+(CH3)2CH2CH2OH, B-For FeCl4 -、FeCl3Br-、GdCl3Br-、GdCl4 -。
2. the method for the preparation side chain type magnetic monomer based on alkylammonium salt as claimed in claim 1, it is characterized in that, select outer 2,3 dicarboxylic anhydrides of cis 5 norborene as raw material, as shown in chemical structure of general formula (II), carry out as steps described below:
Outer for cis 5 norborene 2,3 dicarboxylic anhydrides and amine micromolecular are obtained by reacting the first intermediate product according to equimolar ratio example by step 1;
Step 2, the first intermediate product step 1 obtained and halogenated hydrocarbons carry out quaterisation and obtain the second intermediate product;
Step 3, the second intermediate product step 2 obtained and ion exchange resin carry out ion exchange, obtain the 3rd intermediate product;
Step 4, the 3rd intermediate product step 3 obtained and metal halide obtain magnetic monomer after reacting;
In described step 1, described amine micromolecular is N, N-dimethyl-ethylenediamine, 4-dimethylaminobutylamine, 6-(dimethylamino) hexylamine, 12-(dimethylamino) dodecyl amine, or 2-[[2-[(2-amino-ethyl) amino] ethyl] amino] ethanol; Outer 2,3 dicarboxylic anhydrides of described cis 5 norborene and the micromolecular consumption of amine are equimolar ratio;
In described step 2, described halogenated hydrocarbons is iodomethane; Described halogenated hydrocarbons is excessive, and its consumption is (1 5) with the mol ratio of 2,3 dicarboxylic anhydrides outside cis 5 norborene: 1
In described step 3, described ion exchange resin is chloride ion exchanger resin, bromide ion exchanger resin, utilizes ion exchange resin to provide chloride ion, bromide ion, carries out ion-exchange reactions with the second intermediate product;
In described step 4, described metal halide is ferric chloride, Iron(III) chloride hexahydrate, gadolinium trichloride or six trichloride hydrate gadoliniums; The consumption of described metal halide and the 3rd intermediate product is equimolar ratio.
3. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 1, utilize dichloromethane for reaction dissolvent, it is sufficiently stirred for cis 5 norborene outer 2,3 dicarboxylic anhydrides, amine micromolecular and dichloromethane are uniform to realize system, react cmpletely at 120～130 DEG C, and the response time is 4h at least.
4. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 1, utilize dichloromethane for reaction dissolvent, it is sufficiently stirred for cis 5 norborene outer 2,3 dicarboxylic anhydrides, amine micromolecular and dichloromethane are uniform to realize system, react cmpletely at 120～130 DEG C, and the response time is 4 8h.
5. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 2, utilize oxolane for reaction dissolvent, dissolve the first intermediate product and add halogenated hydrocarbons and react, reacting 2～12h at 25～70 DEG C.
6. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 3, utilize absolute methanol for reaction dissolvent, dissolve the second intermediate product and add ion exchange resin and carry out ion-exchange reactions, reaction system is stirred, at least 4 hours response time at room temperature 20 25 DEG C.
7. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 3, utilize absolute methanol for reaction dissolvent, dissolve the second intermediate product and add ion exchange resin and carry out ion-exchange reactions, reaction system is stirred, the 6 10 hours response time at room temperature 20 25 DEG C.
8. the preparation method of the side chain type magnetic monomer based on alkylammonium salt according to claim 2, it is characterized in that, in described step 4, utilize absolute methanol for reaction dissolvent, dissolve the 3rd intermediate product and add metal halide and react, reacting 8～12h room temperature 20 25 DEG C.
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| CN107663194B (en) * | 2016-07-28 | 2020-06-26 | 天津大学 | Alkyl imidazole tetrahalogenated iron salt substituted biphenyl magnetic liquid crystal monomer and preparation method thereof |
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