CN105037595B - A kind of macromolecule ferrum (III) chelating agen based on 3 hydroxyl 4 pyridine compounds and preparation method thereof - Google Patents
A kind of macromolecule ferrum (III) chelating agen based on 3 hydroxyl 4 pyridine compounds and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of macromolecule ferrum (III) chelating agen based on 3 hydroxyl 4 pyridine compounds and preparation method thereof, methyl propenoic acid glycidyl ether ester containing epoxide group is obtained polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether by radical polymerization, add 3 hydroxyl 4 pyridine compounds containing amido, with epoxide group, ring-opening reaction occurs, it is covalently attached to polymethylacrylic acid glycidyl ether ester side chain and obtain macromolecule ferrum (III) chelating agen, avoid other side reactions, reaction condition is gentle, production safety, process is simple, purification is convenient, yield height (reaching as high as 100%), it is easy to industrialized production.Solve current macromolecule ferrum (III) chelating agen insoluble do not melt, the problems such as ferrum (III) chelating capacity is little, the chelating capacity of ferric ion maximum up to 1196 μm of ol/g.
Description
First, technical field
The present invention relates to a kind of ferrum (III) chelating agen and preparation method thereof, specifically one kind are based on 3- hydroxyl -4- pyrrole
Macromolecule ferrum (III) chelating agen of pyridine ketone compounds and preparation method thereof, belongs to technical field of polymer materials.
2nd, background technology
Macromole iron chelating agent increasingly receives publicity, and medically has certain applied research.Macromolecule iron chelating agent
It is widely used in the fields such as water process, Environmental capacity, metal ion recovery, active packing and analytical chemistry.In recent years, also have
Report the application in biomedical aspect for the macromolecule iron chelating agent material.Ferrum is a kind of very important element to organism,
Capture for ferrum element will have certain application prospect to treatment microbial infectious diseases in theory.ENREF 9 is high
Molecule iron chelating agent can also transship the effectively treatment medicine of disease as some chronic or acute ferrum.Although currently for ferrum
Overload class disease, common remedy measures are using small molecule class medicine, but macromolecule iron chelating agent is treating these diseases
When have some apparent advantages, for example, when high-molecule chelated medicine is administered orally, due to the characteristic meeting such as high molecular molecular weight is big
Such medicine is not absorbed by the body after adsorbing ferrum element in the intestines and stomach, very efficiently will be external for ferrum exclusion.
The U.S.《Journal of applied》(Journal of Applied Polymer Science, 1994 52
Roll up 21-28 page of the 1st phase) use 1- (β-acryloyl ethyl) -3- hydroxy-2-methyl -4- (1H)-pyridone (AHMP) of reporting,
N, N- DMAA, N, N'- vinyl bisacrylamide obtains a kind of polymerization containing 3- hydroxyl -4- pyridinone
Thing, this polymer is insoluble not to be melted.Equally, Britain《European polymer magazine》(European Polymer Journal, 1994
The 8th phase of volume 30, page 941 947) use AHMP, hydroxyethyl methylacrylate and the Ethylene glycol dimethacrylate reported
Obtain a kind of there is cross-linked structure, the insoluble insoluble polymer containing 3- hydroxyl -4- pyridinone.The U.S.《Biomacromolecule》
One kind that (Biomacromolecules, volume 9 the 5th phase page 1,372 1380 in 2008) is reported is based on 3- hydroxyl -4- pyridone
The chelate polymer material of the cross-linked structure of class sexadentate ligand synthesis, is also a kind of insoluble insoluble material, limits such chela
The application of mixture, the material ferrum chelating capacity obtaining very little (271 μm of ol/g).
The U.S.《Polymer science magazine, A collects：Polymer chemistry》(Journal of Polymer Science Part
A:Polymer Chemistry, 2012 volume 50 page 3,493 3498) one kind of reporting is based on 2 hydroxyl first in kojic acid derivative
Base and isocyanates react the method obtaining the polyurethane with chelating ability, but on pyranoid ring in kojic acid, 5 hydroxyls also can
Reaction, not only forms cross-linked structure, and consumes the hydroxyl moieties much doing chelating.Raw material one due to polyurethane reaction
As be isocyanates and diatomic alcohol compounds, isocyanates are very high with hydroxyl reaction activity, pyranone derivatives (as kojic acid,
Maltol etc.), 3- hydroxyl -4- pyridine compounds (such as the compound of trade name Ferriprox, chemical name be 3- hydroxyl -
1,2- dimethyl -4- (1H)-pyridone, can be used for general Fe supply disease, it may also be used for treat some local ferrum element excessive
Distribution) in the hydroxyl containing coordination inevitable react with isocyanates.3- hydroxyl -4- pyridine compounds are compared with pyrrole
Ketone compounds of muttering have higher ferrum affinity ability, according to Holland《Coordinative Chemistry is commented on》(Coordination Chemistry
Reviews, 2002 151-171 page of volume 232) report kojic acid, maltol and 3- hydroxyl -1,2- dimethyl -4- (1H)-pyridine
The pFe of ketoneIIIValue is respectively 14.93,15 and 19, wherein pFeIIIIt is worth for [part]Always=10-5M, [Fe]Always=10-5M, pH=7.4
When, the negative logarithm of free iron (III) ion concentration, value shows that more greatly chelating agen is stronger to ferric ion affinity ability, is formed
Ferrum (III) chelating agent complexes stability higher.
In a word, current synthesis macromolecule iron chelating agent complex steps, the material ferrum chelating capacity obtaining little it is difficult to industrialization
Application.
3rd, content of the invention
The present invention is intended to provide a kind of macromolecule ferrum (III) chelating agen based on 3- hydroxyl -4- pyridine compounds and
Its preparation method, the methyl propenoic acid glycidyl ether ester containing epoxide group is obtained polymethyl by radical polymerization
Acid glycidyl ether-ether, then passes through the upper amido of 3- hydroxyl -4- pyridine compounds and epoxy occurs ring-opening reaction, grafting
To on polymer molecular chain, obtain macromolecule ferrum (III) chelating agen of -4- pyridine compounds of hydroxyl containing 3-, to solve mesh
Front macromolecule ferrum (III) chelating agen is insoluble not to be melted, the problems such as ferrum (III) chelating capacity is little, synthesis step is loaded down with trivial details.
Macromolecule ferrum (III) chelating agen based on 3- hydroxyl -4- pyridine compounds for the present invention, its structure is：
Wherein n=20-200.
The preparation method of macromolecule ferrum (III) chelating agen based on 3- hydroxyl -4- pyridine compounds for the present invention, be by
Methyl propenoic acid glycidyl ether ester containing epoxide group obtains polymethylacrylic acid glycidyl ether by radical polymerization
Ester, adds the 3- hydroxyl -4- pyridine compounds containing amido, with epoxide group, ring-opening reaction occurs, be covalently attached to poly-
Methyl propenoic acid glycidyl ether ester side chain obtains macromolecule ferrum (III) chelating agen；
The preparation of macromolecule ferrum (III) chelating agen includes radical polymerization polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether
The open loop that preparation and polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether and the 3- hydroxyl -4- pyridine compounds containing amido occur
React two step compositions；Wherein radical polymerization process is reversible addion-fragmentation chain transfer polymerization or general radical polymerization
Method.
Prepare the concrete operations of polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether by reversible addion-fragmentation chain transfer polymerization
Step is as follows：
The ratio of the amount of material is 65-100:1:0.3 methyl propenoic acid glycidyl ether ester, 2- cyano group -2- propylbenzene
And two sulfur and azodiisobutyronitrile be added in reactor, be subsequently adding and methyl propenoic acid glycidyl ether ester volume identical
Dry toluene, as solvent, reacts 2-6 hour in 55-70 DEG C in nitrogen atmosphere after removing oxygen, adds dry toluene 10-20
(- 20 DEG C) sedimentations of the cold diethyl ether of times volume, filtration drying removes unreacted methyl afterwards for centrifugation (3000-5000 rev/min)
Glycidyl ether-ether monomer；Add dry toluene isopyknic DMF dissolving macromolecule, add
The cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, after centrifugation drying solid, dissolving, infall process 3-5 time repeatedly, obtains
Polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether.
The concrete operation step preparing polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether by general radical polymerization is as follows：
The ratio of the amount of material is 100-350:1 methyl propenoic acid glycidyl ether ester and azodiisobutyronitrile are added to
In reactor, it is subsequently adding with methyl propenoic acid glycidyl ether ester volume identical dry toluene as solvent, at 55-70 DEG C
After reaction 2-6 hour, add (- 20 DEG C) of the cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, centrifugation (3000-5000 turns/
Minute) remove supernatant afterwards, then it is dried；Add dry toluene isopyknic DMF dissolving macromolecule,
Add the cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, dissolving, infall process 3-5 time repeatedly after centrifugation drying solid,
Obtain polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether.
Described ring-opening reaction comprises the steps：
Polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether (Mn=1000-10000) of 100 mass parts is added in single port bottle,
Be subsequently adding 200-300 mass parts anhydrous DMF dissolving, be subsequently adding 50-100 mass parts triethylamine and
100-1000 mass parts contain the 3- hydroxyl -4- pyridine compounds of amido, keep 55-80 DEG C of reaction 2-36 hour, to anti-
Answer the ether sedimentation products adding 2000-3000 mass parts in liquid, be dried after filtering precipitation, be subsequently adding 200-300 mass parts
Anhydrous DMF dissolving, puts into dialysis in bag filter and (changes No. four distilled water daily, bag filter retains number in 3-5 days
Average molecular weight is 3000-5000) remove the excessive 3- hydroxyl -4- pyridine compounds containing amido, obtain macromolecule ferrum
(III) chelating agen.
The described 3- hydroxyl -4- pyridine compounds containing amido are selected from 1- (amino -4,7,10- three oxygen tridecane
Base) -2- methyl -3- hydroxyl -4- (1H)-pyridone (1), 1- amino-ethyl -2- methyl -3- hydroxyl -4- (1H)-pyridone (2),
1- methylaminopropyl -2- methyl -3- hydroxyl -4- (1H)-pyridone (3) or 2- methyl -3- hydroxyl -4- (1H) -5- methylamino first
Base-pyridone (4), its structural formula is as follows：
The present invention compared with prior art has advantages below：
1st, in macromolecule ferrum (III) chelating agen of the present invention, 3- hydroxyl -4- pyridine compounds are located on polymer lateral chain,
Each repetitive contains a 3- hydroxyl -4- pyridine compounds unit, and polymer small molecular chelator is
Greatly up to 70wt%.
2nd, macromolecule ferrum (III) chelating agen of the present invention be dissolvable in water water and acetone, butanone, N,N-dimethylformamide, two
In first sulfoxide, greatly expand its application in aqueous solution, organic solvent system it is also possible to insoluble insoluble macromolecule is obtained
Ferrum (III) chelating agen.
3rd, the present invention utilizes the epoxide group in polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether and 3- hydroxyl -4- pyridinone
There is ring-opening reaction in amido on compound, covalent bond introduces small molecule chelators, it is to avoid other side reactions, reaction condition temperature
With post processing is simple.
4 present invention incorporates the high response type of polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether, low cost, good hydrophilic property, no
Poison is good with material compatibility, post processing and modified simple the features such as and the high ferrum (III) of 3- hydroxyl -4- pyridine compounds
Affinity ability, the material ferrum chelating capacity obtaining greatly promotes, and is 1196 μm of ol/g to the maximum, in water process, Environmental capacity, metal
There is certain application prospect in the fields such as ion recovery, active packing and analytical chemistry.
5th, preparation method production safety of the present invention, process is simple, purification is convenient, yield height (reaching as high as 100%), is easy to
Industrialized production.
4th, brief description
Polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether PGMA1 and PGMA2 that Fig. 1 is prepared for Example 1 and Example 2 of the present invention
Hydrogen nuclear magnetic resonance spectrogram.
Fu of macromolecule ferrum (III) chelating agen 71,72,73 and 74 that Fig. 2 is prepared for Example 1 and Example 2 of the present invention
Vertical leaf transformation infrared spectrogram.
Fig. 3 is the height measuring ferric ion content and the embodiment of the present invention 1 preparation using ultraviolet visible spectrophotometry
The absorbance graph of a relation of molecule ferrum (III) chelating agen 71 aqueous solution.
Fig. 4 is the height measuring ferric ion content and the embodiment of the present invention 1 preparation using ultraviolet visible spectrophotometry
The absorbance graph of a relation of molecule ferrum (III) chelating agen 81 aqueous solution.
Fig. 5 is the height measuring ferric ion content and the embodiment of the present invention 2 preparation using ultraviolet visible spectrophotometry
The absorbance graph of a relation of molecule ferrum (III) chelating agen 84 aqueous solution.
5th, specific embodiment
Embodiment 1：
In the present embodiment, the preparation process of macromolecule ferrum (III) chelating agen is as follows：
1st, radical polymerization
By 1.292g methyl propenoic acid glycidyl ether ester, 29.965mg 2- cyano group -2- propyl group benzo two sulfur and
6.916mg azodiisobutyronitrile is added in 25mL single port bottle, is subsequently adding 1.2mL dry toluene as solvent, removes oxygen
(process removing oxygen is first in liquid nitrogen, single port bottle to be cooled down 5-10 minute, with oil pump is taken out very after taking out from liquid nitrogen afterwards
Empty 1-2 minute, then passes to nitrogen protection, repeats aforesaid operations three times) react 6 hours in 62 DEG C in nitrogen atmosphere, add
Cold diethyl ether (- 20 DEG C, freeze 20min using the dry ice) sedimentation of 10 times of volumes of dry toluene, is centrifuged (4000 revs/min) mistake afterwards
It is filtered dry the unreacted methyl propenoic acid glycidyl ether ester monomer of dry removal；Add the isopyknic N of dry toluene, N- dimethyl
Formyl amine solvent macromolecule, adds the cold diethyl ether sedimentation of 10 times of volumes of dry toluene, repeatedly dissolve after centrifugation drying solid,
Infall process 3 times, obtains polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether PGMA1.
2nd, ring-opening reaction
The 0.2g PGMA1 that prepare step 1 and 1.3g 1- (amino -4,7,10- three oxygen tridecyl) -2- methyl -3-
Hydroxyl -4- (1H)-pyridone is added in single port bottle, is subsequently adding the dissolving of 8mL anhydrous DMF, adds
1mL triethylamine, keeps 55 DEG C to react 36 hours, adds 80mL ether sedimentation products in reactant liquor, is dried, puts after filtering precipitation
Enter the monomer that in bag filter, dialysis 3 days (changing No. four distilled water daily, bag filter molecular cut off is 3000) removes excess to obtain
Macromolecule ferrum (III) chelating agen 71, the wherein small molecule chelators content in macromolecule ferrum (III) chelating agen is about
70wt%.Take 0.1 gram 71 and be dissolved separately in 1mL water and acetone, butanone, DMF, dimethyl sulfoxide, can be with shape
Become solution, do not have any insoluble matter to leave in the solution.
If keeping other conditions constant, by 1.3g 1- in reactant (amino -4,7,10- tri- oxygen tridecyls) -2- first
Base -3- hydroxyl -4- (1H)-pyridone is replaced by 1g 1- amino-ethyl -2- methyl -3- hydroxyl -4- (1H)-pyridone, can get
Macromolecule ferrum (III) chelating agen 72, the wherein small molecule chelators content in macromolecule ferrum (III) chelating agen is about
54wt%.
If keeping other conditions constant, 0.2g PGMA1 in reactant is replaced by 0.2g PGMA2 prepared by embodiment 2,
Can get macromolecule ferrum (III) chelating agen 81, wherein content in macromolecule ferrum (III) chelating agen for the small molecule chelators is about
70wt%.
If it is constant to keep reaction to feed intake, is reacted using general radical, be added without 2- cyano group -2- propyl group benzo two sulfur, no
Carry out freezing-evacuation-defrosting, equally can obtain polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether.
Characterized by gel permeation chromatography (GPC) and obtain polymer.Using mobile phase be N,N-dimethylformamide, polyphenyl
Ethylene does the polymer of the GPC detection synthesis of standard, and result shows the high molecular M of PGMA1n=12800g mol-1, Mw/Mn=
1.07.
Embodiment 2：
In the present embodiment, the preparation process of macromolecule ferrum (III) chelating agen is as follows：
1st, radical polymerization
By 0.932g methyl propenoic acid glycidyl ether ester, 18 × 10-2G 2- cyano group -2- propyl group benzo two sulfur and
42.53mg azodiisobutyronitrile is added in 25mL single port bottle, is subsequently adding 0.87mL dry toluene as solvent, removes oxygen
(process removing oxygen is first in liquid nitrogen, single port bottle to be cooled down 5-10 minute, with oil pump is taken out very after taking out from liquid nitrogen afterwards
Empty 1-2 minute, then passes to nitrogen protection, repeats aforesaid operations three times) react 3 hours in 62 DEG C in nitrogen atmosphere, add
Cold diethyl ether (- 20 DEG C, freeze 20min using the dry ice) sedimentation of 10 times of volumes of dry toluene, is centrifuged (4000 revs/min) mistake afterwards
It is filtered dry the unreacted methyl propenoic acid glycidyl ether ester monomer of dry removal；Add the isopyknic N of dry toluene, N- dimethyl
Formyl amine solvent macromolecule, adds the cold diethyl ether sedimentation of 10 times of volumes of dry toluene, repeatedly dissolve after centrifugation drying solid,
Infall process 3 times, obtains polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether PGMA2.
2nd, ring-opening reaction
The 0.2g PGMA2 that prepare step 1 and 0.29g 1- methylaminopropyl -2- methyl -3- hydroxyl -4- (1H)-pyridine
Ketone is added in single port bottle, is subsequently adding the dissolving of 8mL anhydrous DMF, adds 1mL triethylamine, keeps 80 DEG C
Reaction 2 hours, adds 80mL ether sedimentation products in reactant liquor, is dried, puts in bag filter and dialyse 3 days after filtering precipitation
(changing No. four distilled water daily, bag filter molecular cut off is 3000) removes excessive monomer and obtains macromolecule ferrum (III) chelating
Agent 83, the wherein small molecule chelators content in macromolecule ferrum (III) chelating agen is about 58wt%, and this reaction yield is
100%.
If keeping other conditions constant, 0.2g PGMA2 in reactant being replaced by 0.2g PGMA1, can get macromolecule
Ferrum (III) chelating agen 73, the wherein small molecule chelators content in macromolecule ferrum (III) chelating agen is about 58wt%.
If keeping other conditions constant, by 0.29g 1- methylaminopropyl -2- methyl -3- hydroxyl -4- (1H) in reactant -
Pyridone is replaced by 0.24g 2- methyl -3- hydroxyl -4- (1H) -5- Methyaminomethyl-pyridone, can get macromolecule ferrum
(III) chelating agen 84, the wherein small molecule chelators content in macromolecule ferrum (III) chelating agen is about 54wt%.
If keeping other conditions constant, by 0.2g PGMA2,0.29g 1- methylaminopropyl -2- methyl -3- in reactant
Hydroxyl -4- (1H)-pyridone is replaced by 0.2g PGMA1,0.24g 2- methyl -3- hydroxyl -4- (1H) -5- methylamino first respectively
Base-pyridone, can get macromolecule ferrum (III) chelating agen 74, wherein small molecule chelators are in macromolecule ferrum (III) chelating agen
Content be about 70wt%.
Using mobile phase be DMF, polystyrene do standard GPC detection synthesis polymer, result
Show the high molecular M of PGMA2n=10300g mol-1, Mw/Mn=1.12.
Application Example：
Select above-described embodiment 1 with 2-in-1 become 71,81 and 84 mensure carrying out ferrum chelating capacity that obtain, to probe into difference
The chelated iron macromolecule of molecular weight lengths, iron ion (III) chelating of macromolecule ferrum (III) chelating agen that different ligands are formed holds
Amount.Concrete operations are as follows：Dried chelated iron fractionated polymer another name is measured (71:4.25mg；81:5.39mg or 84:
6.15mg), it is then respectively adding 0.4mL dimethyl sulfoxide and forms solution, then take a certain amount of above-mentioned solution (71,5 μ L；81,5μ
L or 84,10 μ L) it is added separately to the 1.4mL water formation high molecular aqueous solution of chelated iron (amount of dimethyl sulfoxide is ignored),
By be calculated three kinds of macromolecular compounds 71,81 and 84 concentration be respectively 37.95 μ g/mL, 48.13 μ g/mL and
109.82μg/mL.This experiment adopts ferric chloride in aqueous solution (0.8953mM, FeCl3) titrated, 5 microlitres of chlorine of titration in every 5 minutes
Change water solution, by ultraviolet-visible absorption spectroscopy (250-600nm), the ferrum chelating capacity of compound is measured, because high
After molecular compound and iron ion chelating, there is absorption in visible-range, with the increase of iron chelating agent concentration, ultraviolet-can
See that absorbance increases, when the chelating agen saturation that iron ion and macromolecule are formed, absorbance will no longer change, now can be according to dripping
Plus the cubage of iron ion obtains high molecular ferrum chelating capacity in ferrous solution.
We have found that in the synthetically prepared UV-visible absorption spectrum of macromolecule ferrum (III) chelating agen of the present embodiment
Absorbing peak position first increases at 460nm, then keeps constant.Because the part unit (1 in iron ion and macromolecule:3) shape
Become complex, the absworption peak of this chelating agen at 460nm, with the increase of iron chelating agent in solution, the absorbance of absworption peak by
Cumulative plus, when the ferrum saturation in system, that is, when not having the iron ion that unnecessary ligand sequestration Deca enters system, absorbance will not
Change again, during maximum absorbance, the iron ion total amount of Deca is this high molecular ferrum chelating capacity.
After testing, all of macromolecular material all has very high ferrum chelating capacity, and 71,81 and 84 ferrum chelating capacity is divided
Wei not 843 μm of ol/g, 1196 μm of ol/g and 699 μm of ol/g.It was found that the ferrum sequestering power of part unit is bigger, its conduct
The tfe polymer chelating capacity that reaction monomers obtain is bigger.Current commercialization de-iron macromolecular material, such as Chelex-100
It is a kind of chemical chelating resin being made up of divinylbenzene, styrene copolymer, containing paired Iminodiacetate ion,
Multivalent ion can be chelated, particularly have very high affinity and chelation to high volence metal ion, its ferrum (III) chelating capacity
It is only 110 μm of ol/g.Macromolecular material ferrum (III) chelating capacity of our synthesis is far longer than the macromolecule of document report synthesis
(Biomacromolecules, volume 9 the 5th phase page 1,372 1380 in 2008,271 μm of ol/g) and business-like de-iron macromolecule
Material (Chelex-100).So, this material can be before there be extraordinary application in the fields such as water process, iron in human overload
Scape.
Claims (10)
1. a kind of macromolecule ferrum (III) chelating agen based on 3- hydroxyl -4- pyridine compounds is it is characterised in that its structure
For：
Wherein n=20-200.
2. the system of macromolecule ferrum (III) chelating agen based on 3- hydroxyl -4- pyridine compounds according to claim 1
Preparation Method it is characterised in that：It is that the methyl propenoic acid glycidyl ether ester containing epoxide group is obtained by radical polymerization
Polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether, is added the 3- hydroxyl -4- pyridine compounds containing amido and is sent out with epoxide group
Raw ring-opening reaction, is covalently attached to polymethylacrylic acid glycidyl ether ester side chain and obtains macromolecule ferrum (III) chelating agen.
3. preparation method according to claim 2, including radical polymerization process and ring-opening reaction process, its feature exists
In：
Described radical polymerization process is reversible addion-fragmentation chain transfer polymerization or general radical polymerization；
Described ring-opening reaction process comprises the steps：
The polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether of 100 mass parts is added in single port bottle, is subsequently adding 200-300 mass parts
Anhydrous DMF dissolving, adds the 3- that 50-100 mass parts triethylamine and 100-1000 mass parts contain amido
Hydroxyl -4- pyridine compounds, keep 55-80 DEG C of reaction 2-36 hour, add 2000-3000 mass parts in reactant liquor
Ether sedimentation products, are dried after filtering precipitation, are subsequently adding the dissolving of 200-300 mass parts anhydrous DMF, put
Enter dialysis in bag filter and remove the excessive 3- hydroxyl -4- pyridine compounds containing amido in 3-5 days, obtain macromolecule ferrum
(III) chelating agen.
4. preparation method according to claim 3 it is characterised in that：
The described 3- hydroxyl -4- pyridine compounds containing amido are selected from 1- (amino -4,7,10- three oxygen tridecyl) -2-
Methyl -3- hydroxyl -4- (1H)-pyridone, 1- amino-ethyl -2- methyl -3- hydroxyl -4- (1H)-pyridone, 1- methylamino third
Base -2- methyl -3- hydroxyl -4- (1H)-pyridone or 2- methyl -3- hydroxyl -4- (1H) -5- Methyaminomethyl-pyridone.
5. preparation method according to claim 3 it is characterised in that：
The number-average molecular weight of described polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether is 1000-10000.
6. preparation method according to claim 3 it is characterised in that：
Put into during dialysing 3-5 days in bag filter, change No. four distilled water daily, bag filter retention number-average molecular weight is
3000-5000.
7. preparation method according to claim 3 is it is characterised in that described radical polymerization process is reversible addition-fracture
Chain transfer polymerization method, comprises the steps：
The ratio of the amount of material is 65-100:1:0.3 methyl propenoic acid glycidyl ether ester, 2- cyano group -2- propyl group benzo two
Sulfur and azodiisobutyronitrile are added in reactor, are subsequently adding dry toluene as solvent, remove oxygen anti-after 55-70 DEG C
Answer 2-6 hour, add the cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, after centrifugation, filtration drying removes unreacted first
Base glycidyl ether-ether monomer；Add dry toluene isopyknic DMF dissolving macromolecule, plus
Enter the cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, after centrifugation drying solid, dissolving, infall process 3-5 time repeatedly, obtains
To polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether.
8. preparation method according to claim 7 it is characterised in that：
The volume of solvent dry toluene is identical with methyl propenoic acid glycidyl ether ester volume；
Cold diethyl ether refers to -20 DEG C of ether.
9. preparation method according to claim 3 is it is characterised in that described radical polymerization process gathers for general radical
Conjunction method, comprises the steps：
The ratio of the amount of material is 100-350:1 methyl propenoic acid glycidyl ether ester and azodiisobutyronitrile are added to reaction
In device, it is subsequently adding dry toluene as solvent, after 55-70 DEG C of reaction 2-6 hour, adds 10-20 times of volume of dry toluene
The cold diethyl ether sedimentation of amount, removes supernatant after centrifugation, is then dried；Add the isopyknic N of dry toluene, N- dimethyl formyl
Amine solvent macromolecule, adds the cold diethyl ether sedimentation of 10-20 times of volume of dry toluene, repeatedly dissolve after centrifugation drying solid,
Infall process 3-5 time, obtains polymethylacrylic acid (+)-2,3-Epoxy-1-propanol ether-ether.
10. preparation method according to claim 9 it is characterised in that：
The volume of solvent dry toluene is identical with methyl propenoic acid glycidyl ether ester volume；
Cold diethyl ether refers to -20 DEG C of ether.
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