CN104231141B - A kind of amino nitrogen heterocyclic ring resin and preparation method thereof - Google Patents
A kind of amino nitrogen heterocyclic ring resin and preparation method thereof Download PDFInfo
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- CN104231141B CN104231141B CN201410439072.6A CN201410439072A CN104231141B CN 104231141 B CN104231141 B CN 104231141B CN 201410439072 A CN201410439072 A CN 201410439072A CN 104231141 B CN104231141 B CN 104231141B
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Abstract
The invention provides a kind of azacyclo-amino resin and preparation method thereof, the resin has such as structure, and wherein M is resin matrix, and R can be H, may also be the group with hydroxyl, sulfydryl, ether, thioether group, amide or ester group, but also with Q identical nitrogen heterocyclic rings functional group；Q is nitrogen heterocyclic ring class group, but pyridine radicals, imidazole radicals, piperidyl, indyl etc..The specific functional groups structure of this amino resins, can more effectively improve selective absorption capacity of the resin to target metal ions, can be in hydrometallurgy industry or plating etc. is reclaimed to valuable metal in industry, with the high selectivity to copper ion.
Description
Technical field
The present invention relates to a kind of amino nitrogen heterocyclic ring resin and preparation method thereof, belongs to organic compound technology of preparing neck
Domain.
Background technology
In hydrometallurgy, different kinds of ions deposit in the feed liquid of thumping majority, especially some ionic natures are similar, it is difficult to point
From separating target metal ions from such complicated feed liquid environment, there is very big difficulty always.Resin method due to environmental protection,
The more low factor of process is simple, cost, is gradually favored by people, gradually represents increasing excellent in field of hydrometallurgy
Gesture, but it is also faced with many technical bottlenecks.
Patent US-A 4098867, describes a kind of heterodisperse gel-type chelating resins, and this resin has following structure
Formula is characterized：
M is resin matrix；
Q is-a CH2- group；
Y can be H or C1～C4Alkyl and
R is-CH2COOH；
The technology prepares the crosslinked resin matrix of styrene and divinylbenzene using suspension polymerization, and carries out chloromethyl
Change reaction, prepare chloromethyl resin, the resin with pyridine functional groups for being reacted with aminopyridine afterwards and being generated.
The resin especially has preferably application in the industry such as hydrometallurgy industry or plating to valuable metal to the extraction of copper,
But from the point of view of existing technology, the resin is no longer suitable for substantially；
Patent CN102015107A provides a kind of preparation method of Picolylamine resins, and the resin is suitable for from water
Valuable metal is extracted in solution and is particularly copper, its resin functionality's structure is：
M is resin matrix
R1 is picolyl
R2 is the organic group with functional groups such as thioether, hydroxyl, amino, phosphate esters
M=1～4, n+p=2
The technology is basically identical with resin functionality in 4098867 patented technologies of US-A, using aminomethyl-pyridine conduct
Main functional group, simply manufacture method is different, and specially resin first prepares styrene and divinylbenzene using suspension polymerisation
Copolymerization ball, afterwards with phthalimide method on the phenyl ring of resin matrix on a primary amine functional group, then use chloromethyl
Pyridine prepares the resin with pyridine functional groups with primary amine reaction.
Patent CN102295723A discloses a kind of preparation method of 6- aminopyridine-3-carboxylic acid chelating resins, the method
The following structure of resin functionality of announcement：
In the technology, resin matrix first obtains the copolymerization ball of styrene and divinylbenzene, Zhi Houyong using suspension polymerization
Zinc chloride makees catalyst, and chloromethyl ether is chloromethylation reagents, obtains chloromethyl ball, then reacts with 6- aminopyridine-3-carboxylic acids,
Obtain the said goods.
The technology is reacted with the carboxyl on pyridine ring and chloromethyl resin, protects the amino on pyridine ring, purpose
The amino and metal for enabling pyridine ring is preferably coordinated, and improves the ability of resin absorption metal；Simultaneously make pyridine directly with tree
Methyl on fat is connected, and shortens the distance of pyridine ring and resin, is combined with metal tightr.But the major defect of the technology
That 6- aminopyridine-3-carboxylic acid molecules are larger, it is more difficult with resin-bonded, while the presence of carboxyl make on resin pyridine ring and
The content relative drop of amino, resin absorption capacity will decrease.The resin is mainly used in the gold such as copper in hydrometallurgy industry
The separation and recovery of category.
Nitrogen-containing hetero cyclics have very strong metal-complexing ability, nitrogen heterocyclic ring is particularly pyridine radicals and introduces tree
It is to improve resin metallic binding ability in fat, realizes the detached necessary means of valuable metal.
Resin containing pyridine functional groups has been prepared in patent US-A 4098867 and patent CN102015107A, its
Mainly based on aminomethyl-pyridine base, this structure reduces amino and pyrrole because there is a methyl between amino and pyridine groups
The performance of piperidinyl coordination chelating, so as to affect the coordination ability and absorption property of resin and metal.
Although patent CN102295723A has prepared aminopyridine functional group, but pyridine ring relies on ester with the connection of resin
Key, in strong acid and strong base system, functional group gradually inactivates, and causes absorption property to decline；The connection of ester bond simultaneously makes effective functional group
In resin, accounting is reduced, and adsorption capacity will be affected., there is absorption in the resin prepared by method for adopting in document at present
Poor selectivity, the problems such as absorbability is relatively low.
The content of the invention
The present invention provides a kind of amino nitrogen heterocyclic ring resin, and nitrogen heterocyclic ring is introduced resin, the amino on resin with it is nitrogenous
Heterocycle is directly connected to, and coordinates with the group such as hydroxyl, sulfydryl, ether, thioether group, amide, ester group, can more effectively improve resin
Adsorptive selectivity to target metal ions.
Present invention also offers the purposes of this important new chelating resin, the resin has and existing common chelating
The resin such as different property of phosphoramidic acid class chelating resin, aminocarboxylic acids chelating resin, which can be used in complex environment
The separation of metal ion：Such as with the high selectivity to copper ion, can be from selectivity in the more impurity such as iron content, magnesium, manganese
Absorbing copper etc..Another king-sized feature of the resin can be the selective extraction copper from stronger acid solution.Separately
Outer its shows incompatible characteristic to ferrum, particularly ferric iron, and this kind of characteristic allows resin in high ferric iron environment
Middle selection absorbing copper, without adopting methods such as ferric iron back or precipitations, this not only reduces cost, and has
Preferable operating characteristics.
The amino nitrogen heterocyclic ring resin that the present invention is announced can extract valuable metal from solution, be particularly suitable for molten from acidity
Valuable metal, such as copper are reclaimed in liquid.
The present invention is achieved by the following technical solutions.
Amino nitrogen heterocyclic ring resin of the present invention, with following general structure：
Wherein：M is resin matrix；R can be H, or carry hydroxyl, sulfydryl, ether, thioether group, amide or ester
The group of base, can also be and Q identical nitrogen heterocyclic rings functional group；Q is nitrogen heterocyclic ring class group.
Specifically, the resin matrix M is the copolymer of polystyrene and divinylbenzene, or is phenolic compound and aldehydes
The condensation high polymer of compound.
Specifically, the R is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2O CH3、-CH2CH(OH)CH3、-CH2
(CH2)5OH、-CH2CH2SH、-CH2CH2CH2SH、-CH2CH2S CH2CH3、-CH2CH(SH)CH3、-CH2(CH2)5SH、-CH2CH2
(CO)NH2、-CH2CH2(CO)O CH2CH3。
Specifically, the nitrogen heterocyclic ring is pyridine radicals, indyl, piperidyl or imidazole radicals and its derivant.
More specifically, the Q is Wherein T represents the connection position of nitrogen heterocyclic ring and resin.
The preparation method of amino nitrogen heterocyclic ring resin of the present invention, it is characterised in that comprise the following steps：(1) set
The synthesis of aliphatic radical body first passes through the resin matrix polystyrene bead of suspension polymerisation, synthesizing styrene and divinylbenzene or synthesis phenol
Urea formaldehyde matrix, its structure are as follows：
(2) polystyrene bead Jing Gabriel reactions carry out amination system to phenyl ring with N- hydroxymethylphthalimides
Primary amine resin is obtained, phenolic resin as matrix resin is obtained primary amine resin with organic amine reaction, i.e.,
(3) primary amine resin is reacted with chlorination nitrogen-containing heterocycle compound, and the structure for obtaining isWherein M
It is resin matrix, Q is nitrogen heterocyclic ring class group；
(4) above-mentioned resin further with containing the base such as hydroxyl, sulfydryl, ether, thioether group, amide, ester group and nitrogen heterocyclic ring
Chloride, epoxide or episulfide for rolling into a ball etc. react the resin structure for obtainingWherein M is resin matrix,
Q is nitrogen heterocyclic ring class group, and R can be H, or the base with hydroxyl, sulfydryl, ether, thioether group, amide or ester group
Group, can also be and Q identical nitrogen heterocyclic ring groups.
Specifically, the chlorination nitrogen-containing heterocycle compound is 2- chloropyridines, 2- chlorin-3-amido-4-methyl pyridines, 2,6- bis-
The chloro- 1,3- dimethylimidazoliniuchloride chlorides of chlorin-3-amido-4-methyl pyridine, 2-, the chloro- 7- azaindoles of 4-, 4- Chloperastines.
The solvent used by the reaction of primary amine resin and chlorination nitrogen-containing heterocycle compound is polar solvent, including water, ethanol,
Isopropanol, methanol, dimethyl sulfoxide, dimethoxym ethane, DMF, preferred water or ethanol.
Primary amine resin is 30～90 DEG C with the reaction temperature of chlorination nitrogen-containing heterocycle compound, and preferable temperature is 30～60 DEG C.
The catalysts of primary amine resin and chlorination nitrogen-containing heterocycle compound selected from sodium hydroxide, potassium hydroxide, sodium carbonate,
One kind in potassium carbonate, mass percentage concentration are 20～50%；Preferably 20～50% sodium hydroxide solution.
Primary amine resin is 1 with the mass ratio of aqueous slkali：(0.5～1), primary amine and chlorination nitrogen-containing heterocycle compound in resin
Mol ratio is 1:(1～2).
For primary amine resin and the reaction of chlorination nitrogen-containing heterocycle compound, its preferred feeding mode is first by resin and alkali soluble
Liquid first mixes, then chlorination nitrogen-containing heterocycle compound solution is added, and is particularly added with flowing (continuously flowing into) mode of adding, more favorably
Generate in reaction and product.
Chlorination nitrogen-containing heterocycle compound is configured to into water, ethanol, isopropanol, methanol, dimethyl sulfoxide, first contracting first before reaction
The solution of aldehyde, DMF, is preferably formulated to the solution of water, ethanol, and would be even more beneficial to react is carried out and product
Production.
Chlorination nitrogen-containing heterocycle compound solution can also be configured to its saturated solution.
In preparation process (1), synthesize the polyphenyl of the macropore with cross-linked structure or gel using suspension polymerization
Ethylene ball, cross-linking agent used are common divinylbenzene, by divinylbenzene and cinnamic addition, adjust resin
The degree of cross linking, the currently preferred degree of cross linking are 6～8%.In order to obtain macroporous structure, the present invention is added in monomer
Oil soluble material, such as gasoline, toluene, dimethylbenzene, liquid wax, white oil, hexamethylene, isobutyltrimethylmethane., heptane etc., some are commonly used in the art
Porogen, according to porogen and the ratio of monomer, the structure of adjusting hole, currently preferred porogen are toluene, preferred to cause
Agent addition in hole is 70～100%.
Its structure is as follows：
Step (2) is introduced into primary amine group in polystyrene ball using Gabriel synthetic methods.Polystyrene ball first
Moisture should be first removed, the water in polystyrene spheres micropylar canal be distilled off by the way of drying, water content is generally required
Control in relatively low level, such as less than 3% or lower；Then the polystyrene ball after drying is carried out with solvent it is swelling,
Its objective is to make the duct of resin become able to be reacted reactant, while the solvent should be able to dissolve primary amineization examination
Agent.Common primary amination reagent adopts imide analog compounds, such as N- hydroxymethylphthalimides.
The general selection chlorohydrocarbon of solvent, is usually used chloroform, dichloroethanes, chloroisopropane, chloro n-propane etc., dries
Polystyrene ball after dry preferably selects to be 1 with the mass volume ratio of solvent:2～1：5.Catalyst can use dense sulfur
Acid, anhydride or the proper ratio of the two, the chemical constitution for obtaining are as follows：
Specific preparation method is as follows：
N- hydroxymethylphthalimides, acetic anhydride, dichloroethanes are mixed and carried out temperature reaction first, N- hydroxyl first is made
Base phthalimide is converted to the ester of N- hydroxymethylphthalimides.The process preferably proportioning is that N- methylols are adjacent
Phthalimide：Acetic anhydride：The mass ratio of dichloroethanes is：1:(0.4～0.7):(3～5).Reaction temperature preferably selects 60
～90 DEG C；
Above-mentioned solution is cooled to into less than 30 DEG C afterwards, the polystyrene ball after drying is added, under stirring, is started Deca
Concentrated sulphuric acid, during all the time control system temperature should be less than 30 DEG C.Concentrated sulphuric acid is catalyst in the course of reaction, it is impossible to plus
Too fast, otherwise reaction will more difficult control.After dripping sulphuric acid, high-temperature, insulation reaction are risen, you can obtain containing N- alkyl neighbour's benzene
The resin of dicarboximide group.Preferred reaction temperature is 60～90 DEG C, and preferred reaction time is 10～25h.
Then use strong base solution, it is generally preferable to alkyl phthalic containing N- of 20～30% sodium hydroxide to above-mentioned generation
The resin of imide group is hydrolyzed, hydrolysis adopt High Temperature High Pressure, preferred temperature at 150～180 DEG C, when preferably reacting
Between in 10～25h, preferred sodium hydroxide solution is 1 with the mass ratio of the group resin of alkyl phthalic imide containing N-:
1.Reaction is finished product strainer filtering, water washing, and the resin matrix containing primary amine functional group is obtained after being filtered dry.
After above-mentioned reaction, the success of polystyrene ball and grafting of primary amines obtain polystyrene primary amine resin.The resin
With weak base exchange capacity, the performance of the resin, weak base exchange capacity preferably 3～10mmol/g are evaluated typically with exchange capacity.
Can also be using phenolic resin as resin matrix, from commercially available 122 (II type) faintly acid phenolic aldehyde in step (1)
Cation exchanger resin, its structure are as follows：
In step (2), 122 (II type) faintly acid phenolic type cation exchange resin is changed into into the base with primary amine group
Body, main method are now to dry resin, and making which be warming up to more than 130 DEG C with the ethanol solution of ethylenediamine afterwards is carried out instead
Should, the carboxyl of the resin is changed into into amide, the resin structure for obtaining is as follows：
The resin for obtaining in aforementioned manners, its weak base exchange capacity are 3～5mmol/g.
In step (3), nitrogen heterocyclic ring is introduced into resin, chlorination nitrogen-containing heterocycle compound, such as 2- chloropyridines, 2- can be adopted
Chlorin-3-amido-4-methyl pyridine, bis- chlorin-3-amido-4-methyl pyridines of 2,6-, the chloro- 1,3- dimethylimidazoliniuchloride chlorides of 2-, 4-
Chloro- 7- azaindoles, 4- Chloperastines etc., such compound is easily reacted with primary amine, and under the catalytic action of alkali, chlorination is nitrogenous
Chlorine in heterocyclic compound is combined production hydrogen chloride with the hydrogen in primary amine, while primary amine groups form stable chemical combination with azacyclo-
Thing.The present invention is that azacyclo- is introduced resin using the response characteristic.
Azacyclo- is introduced resin by the present invention, needs to control the addition of raw material chlorination nitrogen-containing heterocycle compound, if chlorine
Change molal quantity of the nitrogen-containing heterocycle compound molal quantity more than primary amine in polystyrene primary amine resin, it will make polystyrene primary amine tree
Primary amine in fat forms secondary amine, tertiary amine, the mixed style of quaternary amine, and the purpose of the present invention is to make primary amine form specific secondary amine or uncle
Amine, quaternary amine would is that invalid group in terms of METAL EXTRACTION recovery.In order to be able to realize this purpose, the present invention is according to primary amine, secondary
The reaction complexity of amine, tertiary amine and chlorination nitrogen-containing heterocycle compound, controls the concentration of chlorination nitrogen-containing heterocycle compound, so as to drop
The forming amount of low quaternary amine.According to response characteristic, the active highest of general primary amine, next to that secondary amine, is tertiary amine again.Thus we
To be gradually added into, i.e., the chlorination nitrogen heterocyclic ring in addition solution understands elder generation and primary to the feed postition of selective chlorination nitrogen-containing heterocycle compound
Amine reacts, after the primary amine in polystyrene primary amine resin is reacted completely, chlorination nitrogen-containing heterocycle compound just can further with
Secondary amine reacts, the like.That is this reaction uses staged reaction.The present invention is by Theoretical Calculation, control simultaneously
The addition of chlorination nitrogen-containing heterocycle compound processed reaches the transformation form of control primary amine to control, and typically preferably chlorination is nitrogenous
Heterocyclic compound should be higher by 10～30% preferably than theoretical amount.
To make the primary amine reaction in chlorination nitrogen-containing heterocycle compound and polystyrene primary amine resin, need to add alkali as urging
Agent, it is possible to use catalyst have sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc., preferred sodium hydroxide.Solvent can
To select to dissolve the solvent of chlorination nitrogen-containing heterocycle compound, it is possible to use water, ethanol, isopropanol, methanol, dimethyl sulfoxide,
Dimethoxym ethane, DMF etc.；Reaction temperature is controlled at 50 DEG C or so.
The chlorination nitrogen-containing heterocycle compound that the present invention is selected preferably can be dissolved in water or ethanol, if do not dissolved in
Water can select its hydrochlorate；Classical way is that polystyrene primary amine resin is put into reaction first in embodiments of the present invention
In kettle, then 20%～50% liquid caustic soda solution being added in reactor, open stirring, the concentration of liquid caustic soda is preferably 20～
30%, primary amine resin is controlled 1 with the mass ratio of liquid caustic soda solution：(0.5～1).
The temperature of control reactor so as between 30～90 DEG C, preferred temperature are 30～60 DEG C.Chlorination is nitrogenous
Heterocyclic compound is dissolved in solvent, is preferably dissolved in water or ethanol, and it is molten that the solution of chlorination nitrogen-containing heterocycle compound should be saturation
Liquid preferably, its objective is to make chlorination nitrogen-containing heterocycle compound after reactor is added, and its concentration is higher, is so easier and tree
Primary amine group on fat is reacted, and another benefit can be that the ingredient proportion for making resin increases, the bar of same reactor
Under part, the increase of resin load.Afterwards chlorination nitrogen-containing heterocycle compound solution is entered in reactor in the way of flowing and adding, stream adds
When should control temperature, make reaction temperature maintain 30～60 DEG C for excellent, be preferred with 2～5h between the stream added-time.Chlorination nitrogen heterocyclic ring
The addition of compound should be calculated with the amount of primary amine in resin, and primary amine is 1 with the mol ratio of chlorination nitrogen-containing heterocycle compound：(1～
2).After completion of dropping, should continue to be kept stirring for, and maintain the temperature at 30～60 DEG C to continue 15～20h of reaction, wash afterwards or use
Solvent washes clean is sloughed free water and nitrogen heterocyclic ring resin intermediate is obtained by ethanol.It is by taking styryl structures as an example, nitrogenous
Heterocyclic compound is assumed to be 2- chloropyridines, then after reacting, resin structure is：
The intermediate again with the chloride containing groups such as hydroxyl, sulfydryl, ether, thioether group, amide and ester groups or other
The reactant for easily being reacted with amine is reacted, so as to obtain band just like-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2O
CH3、-CH2CH(OH)CH3、-CH2(CH2)5OH、-CH2CH2SH、-CH2CH2CH2SH、-CH2CH2S CH2CH3、-CH2CH(SH)
CH3、-CH2(CH2)5SH、-CH2CH2(CO)NH2、-CH2CH2(CO)O CH2CH3Deng the resin of group, resin as of the invention
Finished product, so that 2-chloroethyl alcohol is reacted with above-mentioned nitrogen heterocyclic ring resin intermediate as an example, the nitrogen heterocyclic ring resin of the present invention for obtaining
The structural representation of product is as follows：
Preparation method of the present invention is simple, it is easy to industrialized production, mild condition, gained amino nitrogen heterocyclic ring resin, relatively
Common metal-chelator, can more effectively improve adsorptive selectivity of the resin to target metal ions.Can be particularly used for
Separation to metal ion in complex environment：Such as with the selectivity high to copper ion, can be more miscellaneous from iron content, magnesium, manganese etc.
Selective absorption copper etc. in matter.And incompatible characteristic is shown to ferric iron so that the resin can be in high ferric iron
Selective absorption copper in environment, without adopting methods such as ferric iron back or precipitations, this not only reduces cost, and
And with very useful operating characteristics.
Specific embodiment
Embodiment 1
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to
Hydroxyethyl cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Use dried burning
Cup weighs 80% divinylbenzene 8.8g and styrene 91.2g, adds toluene 80g, dibenzoyl peroxide 0.8g, stirs
After be added in 1000ml reactors, stand 10min, mixing speed is stirred and is adjusted in unlatching, make oil phase be separated into 0.2～
The spherical particle of 0.7mm, is warming up to 80 DEG C of insulation 3h, is warming up to 90 DEG C and continues reaction 5h after ball solidification.After reaction terminates,
Cured ball is filtered out, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane,
Obtain resin matrix 196g.
The ball of the solidification of above-mentioned preparation is put in into 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if be less than
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry until water content is qualified.Done
Resin 102g.
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and added in reactor
Dichloroethanes 200g, acetic anhydride 30g, hydroxyl imines 70g, concentrated sulphuric acid 30g, unlatching stir and are warming up to back flow reaction 20h, lower the temperature, mistake
Ball is leached, is washed with dimethoxym ethane, be washed with water and wash, obtain resin 185g.
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, is warming up to 170
DEG C reaction 10h, filters washing and obtains primary amine resin 143g, and it is 6.8mmol/g to determine weak base friendship amount.
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and 25% hydroxide is added in reactor
Sodium solution 50g, isopropanol 60g, stir and are warming up to 40 DEG C；2- chloropyridine 45g streams are added in 500ml reactors, Jing 4h
Stream adds complete, is warming up to 55 DEG C afterwards, reacts 20h, terminates, filters out resin, and with washing with alcohol, washing obtains azepine containing pyridine
Ring resin 133g.
Above-mentioned resin is weighed into 100g, 500ml glass reaction kettles are put into, 100g water and 0.8g tetraethyl brominations is added
Ammonium, is warming up to 30 DEG C, and by allyl sulfides 40g, stream is added in reactor in the 3h, is warming up to 40 DEG C of reaction 5h afterwards, terminates anti-
Should, Jing washing with alcohol, washing obtain a kind of amino nitrogen heterocyclic ring resin 134g.
Through its structure of naval stores obtained in above-mentioned reaction it is：
The product is evaluated, the resin is 0.72mmol/g to the chelating amount of copper.
Embodiment 2
With commercially available 122 resin, it is baked to, water content 0.8%.Drying resin 80g is weighed, tri- mouthfuls of glass of 1000ml are added to
In glass reactor, ethylene glycol 400ml is added, open stirring, swelling 1h adds ethylenediamine 300ml, is warming up to 150 DEG C of reactions
15h, leaches resin and is washed to neutrality, obtains 267g primary amine phenolic resin.
Above-mentioned primary amine phenolic resin 100g is weighed, is added in tri- mouthfuls of glass reaction kettles of 500ml, with 4- Chloperastine hydrochloric acid
Salt, and 35% potassium hydroxide solution 60g is added in reactor, stir and be warming up to 40 DEG C；4- Chloperastine hydrochlorates will be contained
The common 60g streams of aqueous solution of 32g are added in 500ml reactors, and Jing 5h streams add complete, are warming up to 60 DEG C afterwards, react 18h, knot
Beam, filters out resin, with washing with alcohol, washes and obtains the resin 108g of azacyclo- containing piperidines.
Above-mentioned resin is weighed into 100g, 500ml glass reaction kettles are put into, 100g water and 0.6g tetraethyl brominations is added
Ammonium, is warming up to 30 DEG C, and by expoxy propane 18g, stream is added in reactor in the 4h, is warming up to 45 DEG C of reaction 8h afterwards, terminates anti-
Should, Jing washing with alcohol, washing obtain another amino nitrogen heterocyclic ring resin 106g.
Through its structure of naval stores obtained in above-mentioned reaction it is：
The product is evaluated, the resin is 0.5mmol/g to the chelating amount of copper.
Embodiment 3
Preparation method according to embodiment 1 prepares primary amine resin, but in its preparation process, raw material has following adjustment：
80% divinylbenzene dosage 7.5g, styrene dosage are 92.5g, and toluene dosage is 100g, and other raw materials are constant.The primary amine for obtaining
Resins exchange amount be 7mmol/g, water content 57.23%.
Primary amine resin 100g of above-mentioned preparation is added in 500ml reactors, and add 50% sodium carbonate 90g, open
Open stirring；2- chloro- 1,3- dimethylimidazoliniuchloride chlorides 65.7g are configured to into water saturation solution, stream is added into anti-within the 6h
In answering kettle, 30 DEG C of reaction 35h are warming up to afterwards, ethanol is washed, and the resin 149g of azacyclo- containing imidazoles is obtained after washing.
Above-mentioned resin 100g is taken, is dried in being placed on baking oven, is put in 500ml reactors afterwards, add the 3- of 74g
Chloropropionate, is warming up to 160 DEG C and is at reflux state, react 10h.After reaction terminates, resin, Jing acetone, second are leached
Alcohol is washed, and washing obtains another amino nitrogen heterocyclic ring resin 164g, and resin structure is as follows：
The product is evaluated, the resin is 0.57mmol/g to the chelating amount of copper.
Embodiment 4
Preparation method according to embodiment 1 prepares primary amine resin, but in its preparation process, raw material has following adjustment：
80% divinylbenzene dosage 10g, styrene dosage are 90g, and toluene dosage is 120g, and other raw materials are constant.The primary amine tree for obtaining
Ester exchange amount be 6.5mmol/g, water content 56.17%.
Primary amine resin 100g of above-mentioned preparation is added in 500ml reactors, and add 20% potassium carbonate 80g, open
Stirring is opened, 50 DEG C are warming up to；4- chloro- 7- azaindole 59.4g are configured to into the saturated solution of DMF, in 6h
Within stream add in reactor, be warming up to 60 DEG C of reaction 20h afterwards, DMF washes, and the resin of azacyclo- containing indole is obtained after washing
141g。
Above-mentioned resin 100g is taken, is put in 500ml reactors, add 20% sodium hydroxide solution 70g, add 66g's
3- chlorine propionic acid amide .s, are warming up to 60 DEG C of reaction 18h.After reaction terminates, resin is leached, washing obtains another amino nitrogen heterocyclic ring tree
Fat 148g, resin structure are as follows：
The product is evaluated, the resin is 0.54mmol/g to the chelating amount of copper.
Embodiment 5
Preparation method according to embodiment 4 prepares primary amine resin.
Primary amine resin 100g of above-mentioned preparation is added in 500ml reactors, and add 30% sodium hydroxide 80g,
Stirring is opened, 60 DEG C are warming up to；2,6-, bis- chlorin-3-amido-4-methyl pyridine 70.7g are configured to into the saturated solution of ethanol,
Within 5h, stream is added in reactor, is warming up to 90 DEG C of reaction 5h afterwards, and washing with alcohol obtains the tree of azacyclo- containing pyridine after washing
Fat 154g.
Above-mentioned resin 100g is taken, is placed in baking oven and is dried, put in 500ml reactors, add 2- chloroethylethyl sulfur
Ether 120g, is warming up to 155 DEG C of back flow reaction 14h.After reaction terminates, resin is leached, washing with acetone, washing with alcohol, washing are obtained
Another amino nitrogen heterocyclic ring resin 152g, resin structure are as follows：
The product is evaluated, the resin is 0.54mmol/g to the chelating amount of copper.
Embodiment 6
Preparation method according to embodiment 4 prepares primary amine resin.
Primary amine resin 100g of above-mentioned preparation is added in 500ml reactors, and add 50% sodium hydroxide 100g,
Ethanol 75g, opens stirring, is warming up to 75 DEG C；2- chlorin-3-amido-4-methyl pyridine 66g are configured to into the saturated solution of ethanol,
Stream is added in reactor within the 10h, is warming up to 78 DEG C of back flow reaction 20h afterwards, and acetone is washed, obtained containing pyridine nitrogen after washing
Heterocycle resin 140g.
Above-mentioned resin 100g is taken, is placed in baking oven and is dried, put in 500ml reactors, add 2- chloroethyl methyl ethers
120g, is warming up to 90 DEG C of reaction 18h.After reaction terminates, resin is leached, washing obtains another amino nitrogen heterocyclic ring resin
133g, resin structure are as follows：
The product is evaluated, the resin is 0.57mmol/g to the chelating amount of copper.
Embodiment 7
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to
Hydroxyethyl cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Use dried burning
Cup weighs 80% divinylbenzene 7.5g and styrene 92.5g, adds toluene 100g, dibenzoyl peroxide 0.8g, and stirring is equal
Be added to after even in 1000ml reactors, stand 10min, mixing speed is stirred and adjusted in unlatching, make oil phase be separated into 0.2～
The spherical particle of 0.7mm, is warming up to 80 DEG C of insulation 3h, is warming up to 90 DEG C and continues reaction 5h after ball solidification.After reaction terminates,
Cured ball is filtered out, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane,
Obtain resin 196g.
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if low
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry qualified up to water content, obtain
Dried resin 102g.
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and added in reactor
Dichloroethanes 200g, acetic anhydride 30g, hydroxyl imines 70g, concentrated sulphuric acid 30g, unlatching stir and are warming up to back flow reaction 20h, lower the temperature, mistake
Ball is leached, is washed with dimethoxym ethane, be washed with water and wash, obtain resin 184g.
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, is warming up to 170
DEG C reaction 10h, filters washing and obtains primary amine resin 147g, and it is 7mmol/g to determine weak base friendship amount, water content 57.54%.
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and 25% hydroxide is added in reactor
Sodium solution 60g, ethanol 80g, stir and are warming up to 50 DEG C；2- chloropyridine 82g streams are added in 500ml reactors, Jing 8h streams
Complete, 50 DEG C of insulation afterwards is added, 27h is reacted, is terminated, filter out resin, with washing with alcohol, wash and a kind of amino is obtained containing pyridine
Azacyclo- resin 148g.
Through its structure of naval stores obtained in above-mentioned reaction it is：
The product is evaluated, the resin is 0.84mmol/g to the chelating amount of copper.
Embodiment 8
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to
Hydroxyethyl cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Use dried burning
Cup weighs 80% divinylbenzene 7.5g and styrene 92.5g, adds toluene 100g, dibenzoyl peroxide 0.8g, and stirring is equal
Be added to after even in 1000ml reactors, stand 10min, mixing speed is stirred and adjusted in unlatching, make oil phase be separated into 0.2～
The spherical particle of 0.7mm, is warming up to 80 DEG C of insulation 3h, is warming up to 90 DEG C and continues reaction 5h after ball solidification.After reaction terminates,
Cured ball is filtered out, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane,
Obtain resin 196g.
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if low
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry qualified up to water content, obtain
Dried resin 102g.
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and added in reactor
Dichloroethanes 200g, acetic anhydride 30g, hydroxyl imines 70g, concentrated sulphuric acid 30g, unlatching stir and are warming up to back flow reaction 20h, lower the temperature, mistake
Ball is leached, is washed with dimethoxym ethane, be washed with water and wash, obtain resin 184g.
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, is warming up to 180
DEG C reaction 10h, filters washing and obtains primary amine resin 147g, and it is 7mmol/g to determine weak base friendship amount, water content 57.54%.
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and 25% hydrogen-oxygen is added in reactor
Change sodium solution 60g, ethanol 80g, stir and be warming up to 50 DEG C；2- chloropyridine 40g streams are added in 500ml reactors, Jing 8h
Stream adds complete, 50 DEG C of insulation afterwards, reacts 27h, terminates, filter out resin, with washing with alcohol, washes and obtains azacyclo- containing pyridine
Resin 130g.
Above-mentioned resin is weighed into 100g, 500ml glass reaction kettles are put into, 100g water and 0.96g tetraethyl brominations is added
Ammonium, is warming up to 30 DEG C, and by allyl sulfides 52g, stream is added in reactor in the 3h, is warming up to 40 DEG C of reaction 5h afterwards, terminates anti-
Should, Jing washing with alcohol, washing obtain another kind of amino nitrogen heterocyclic ring resin 144g.
Through its structure of naval stores obtained in above-mentioned reaction it is：
The product is evaluated, the resin is 0.82mmol/g to the chelating amount of copper.
Embodiment 9
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to
Hydroxyethyl cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Use dried burning
Cup weighs 80% divinylbenzene 7.5g and styrene 92.5g, adds toluene 100g, dibenzoyl peroxide 0.8g, and stirring is equal
Be added to after even in 1000ml reactors, stand 10min, mixing speed is stirred and adjusted in unlatching, make oil phase be separated into 0.2～
The spherical particle of 0.7mm, is warming up to 80 DEG C of insulation 3h, is warming up to 90 DEG C and continues reaction 5h after ball solidification.After reaction terminates,
Cured ball is filtered out, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane,
Obtain resin 196g.
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if low
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry qualified up to water content, obtain
Dried resin 102g.
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and added in reactor
Dichloroethanes 200g, acetic anhydride 30g, hydroxyl imines 70g, concentrated sulphuric acid 30g, unlatching stir and are warming up to back flow reaction 20h, lower the temperature, mistake
Ball is leached, is washed with dimethoxym ethane, be washed with water and wash, obtain resin 184g.
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, is warming up to 160
DEG C reaction 10h, filters washing and obtains primary amine resin 147g, and it is 7mmol/g to determine weak base friendship amount, water content 57.54%.
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and 25% hydroxide is added in reactor
Sodium solution 60g, ethanol 80g, stir and are warming up to 50 DEG C；2- chloropyridine 40g streams are added in 500ml reactors, Jing 8h streams
Complete, 50 DEG C of insulation afterwards is added, 27h is reacted, is terminated, filter out resin, with washing with alcohol, washed and obtain the tree of azacyclo- containing pyridine
Fat 130g.
Above-mentioned resin 100g is taken, is put in 500ml reactors, add 100g water and 0.8g tetraethylammonium bromides, heated up
To 30 DEG C, by expoxy propane 41g, stream is added in reactor in the 3h, is warming up to 40 DEG C of reaction 5h afterwards, is terminated reaction, Jing second
Alcohol is washed, and washing obtains another kind of amino nitrogen heterocyclic ring resin 137g.
Through its structure of naval stores obtained in above-mentioned reaction it is：
The product is evaluated, the resin is 0.85mmol/g to the chelating amount of copper.
Claims (15)
1. a kind of amino nitrogen heterocyclic ring resin, it is characterised in that structure is shown below：
Wherein：M is resin matrix,
The resin matrix M is the copolymer of polystyrene and divinylbenzene, or high with the polycondensation of aldehyde compound for phenolic compound
Polymers；The R is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2OCH3、-CH2CH(OH)CH3、-CH2(CH2)5OH、-CH2CH2SH、-
CH2CH2CH2SH、-CH2CH2S CH2CH3、-CH2CH(SH)CH3、-CH2(CH2)5SH、-CH2CH2(CO)NH2、-CH2CH2(CO)O
CH2CH3；The Q is
Wherein T represents the connection position of nitrogen heterocyclic ring and resin.
2. a kind of preparation method of amino nitrogen heterocyclic ring resin, it is characterised in that comprise the following steps：(1) conjunction of resin matrix
Into the resin matrix polystyrene bead or polycondensation novolak resin that first pass through suspension polymerisation, synthesizing styrene and divinylbenzene
Matrix, its structure are as follows：
(2) polystyrene bead Jing Gabriel reactions carry out amination and are obtained primary with N- hydroxymethylphthalimides to phenyl ring
Polyimide resin, phenolic resin as matrix resin are obtained primary amine resin with organic amine reaction, i.e.,
(3) primary amine resin is reacted with chlorination nitrogen-containing heterocycle compound, and the structure for obtaining isWherein M is tree
Aliphatic radical body, Q are nitrogen heterocyclic ring class group；
(4) above-mentioned resin further with the chlorine containing hydroxyl, sulfydryl, ether, thioether group, amide, ester group or nitrogen heterocyclic ring group
Compound, epoxide or episulfide react the resin structure for obtainingWherein M is resin matrix, and Q is nitrogenous
Heterocyclic group, R are the group with hydroxyl, sulfydryl, ether, thioether group, amide or ester group, or with Q identical nitrogen heterocyclic rings
Functional group.
3. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that prepare in step (1)
During polystyrene bead, the degree of cross linking for controlling resin matrix is 6～8%.
4. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that the chlorination is nitrogenous
Heterocyclic compound is 2- chloropyridines, 2- chlorin-3-amido-4-methyl pyridines, bis- chlorin-3-amido-4-methyl pyridines of 2,6-, 2- chloro-
The chloro- 7- azaindoles of 1,3- dimethylimidazoliniuchloride chlorides, 4- or 4- Chloperastines.
5. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that primary amine resin and chlorine
The solvent that used of reaction for changing nitrogen-containing heterocycle compound is polar solvent, including water, ethanol, isopropanol, methanol, dimethyl are sub-
Sulfone, dimethoxym ethane or DMF.
6. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that primary amine resin with
The reaction temperature of chlorination nitrogen-containing heterocycle compound is 30～90 DEG C.
7. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that primary amine resin and chlorine
Change the one kind of the catalysts of nitrogen-containing heterocycle compound in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, quality
Percentage concentration is 20～50%.
8. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 7, it is characterised in that the catalyst is
Mass percentage concentration is 20～50% sodium hydroxide solution.
9. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 7, it is characterised in that primary amine resin and chlorine
Change the reaction of nitrogen-containing heterocycle compound, its feeding mode is for first by resin and sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate
First mix, then chlorination nitrogen-containing heterocycle compound is added.
10. a kind of preparation method of amino nitrogen heterocyclic ring resin according to claim 7, it is characterised in that primary amine resin with
The mass ratio of aqueous slkali sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate is 1：(0.5～1), in resin, primary amine is contained with chlorination
The mol ratio of nitrogen heterocyclic is 1:(1～2).
A kind of 11. preparation methoies of amino nitrogen heterocyclic ring resin according to claim 7, it is characterised in that primary amine resin with
The reaction of chlorination nitrogen-containing heterocycle compound, chlorination nitrogen-containing heterocycle compound are first configured to water, ethanol, isopropanol, methanol, dimethyl
The solution of sulfoxide, dimethoxym ethane or DMF.
12. according to claim 11 a kind of preparation method of amino nitrogen heterocyclic ring resin, it is characterised in that chlorination nitrogen-containing hetero
Cycle compound solution is saturated solution.
13. a kind of preparation methoies of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that the chlorination is nitrogenous
Heterocyclic compound is 2- chloropyridines, 2- chlorin-3-amido-4-methyl pyridines, bis- chlorin-3-amido-4-methyl pyridines of 2,6-, 2- chloro-
The chloro- 7- azaindoles of 1,3- dimethylimidazoliniuchloride chlorides, 4-, 4- Chloperastines；Primary amine resin and chlorination nitrogen-containing heterocycle compound
The used solvent of reaction is water, ethanol, isopropanol, methanol, dimethyl sulfoxide, dimethoxym ethane or DMF；Instead
Temperature is answered to be 30～90 DEG C；Catalysts are selected from following aqueous slkali：In sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
One kind, mass concentration are 20～50%；Primary amine resin is 1 with the mass ratio of aqueous slkali：(0.5～1), primary amine and chlorine in resin
The mol ratio for changing nitrogen-containing heterocycle compound is 1:(1～2)；First resin is mixed with aqueous slkali when feeding intake, then by chlorination nitrogen-containing hetero
The saturated solution of cycle compound is added.
14. according to a kind of preparation method of the arbitrary described amino nitrogen heterocyclic ring resin of claim 2-13, it is characterised in that institute
Chlorination nitrogen-containing heterocycle compound is stated for 2- chloropyridines, 2- chlorin-3-amido-4-methyl pyridines, bis- chloro- 3- amino -4- methyl of 2,6-
The chloro- 1,3- dimethylimidazoliniuchloride chlorides of pyridine, 2-, the chloro- 7- azaindoles of 4-, 4- Chloperastines；Primary amine resin and chlorination nitrogen-containing hetero
The solvent used by the reaction of cycle compound is water or ethanol；Reaction temperature is 30～60 DEG C；Catalysts are quality percentage
Concentration is 20～50% sodium hydroxide solution；Primary amine resin is 1 with the mass ratio of aqueous slkali：(0.5～1), primary amine in resin
Mol ratio with chlorination nitrogen-containing heterocycle compound is 1:(1～2)；First resin is first mixed with aqueous slkali when feeding intake, then by chlorination
The saturated solution of the water or ethanol of nitrogen-containing heterocycle compound is added.
15. a kind of preparation methoies of amino nitrogen heterocyclic ring resin according to claim 2, it is characterised in that including following step
Suddenly：
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to hydroxyl second
Base cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Claimed with dried beaker
80% divinylbenzene 7.5g and styrene 92.5g are taken, toluene 100g, dibenzoyl peroxide 0.8g, after stirring is added
It is added in 1000ml reactors, stands 10min, unlatching is stirred and adjusted mixing speed, makes oil phase be separated into 0.2～0.7mm
Spherical particle, be warming up to 80 DEG C insulation 3h, after ball solidification after be warming up to 90 DEG C continue reaction 5h；After reaction terminates, filter
Go out cured ball, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane, obtains
Resin 196g；
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if be less than
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry up to water content is qualified and done
Resin；
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and dichloro is added in reactor
Ethane 200g, acetic anhydride 30g, N- hydroxymethylphthalimide 70g, concentrated sulphuric acid 30g, unlatching are stirred and are warming up to backflow instead
20h is answered, is lowered the temperature, is filtered out ball, washed with dimethoxym ethane, be washed with water and wash, obtain resin；
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, 170 DEG C is warming up to instead
10h is answered, washing is filtered and is obtained resin；
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and in reactor, add 25% sodium hydroxide molten
Liquid 60g, ethanol 80g, stir and are warming up to 50 DEG C；2- chloropyridine 82g streams are added in 500ml reactors, Jing 8h streams are added
Finish, be incubated 50 DEG C afterwards, react 27h, terminate, filter out resin, with washing with alcohol, wash and obtain resin；
Through its structure of naval stores obtained in above-mentioned reaction it is：
Or：
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to hydroxyl second
Base cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Claimed with dried beaker
80% divinylbenzene 7.5g and styrene 92.5g are taken, toluene 100g, dibenzoyl peroxide 0.8g, after stirring is added
It is added in 1000ml reactors, stands 10min, unlatching is stirred and adjusted mixing speed, makes oil phase be separated into 0.2～0.7mm
Spherical particle, be warming up to 80 DEG C insulation 3h, after ball solidification after be warming up to 90 DEG C continue reaction 5h；After reaction terminates, filter
Go out cured ball, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane, obtains
Resin；
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if be less than
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry up to water content is qualified and done
Resin；
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and dichloro is added in reactor
Ethane 200g, acetic anhydride 30g, N- hydroxymethylphthalimide 70g, concentrated sulphuric acid 30g, unlatching are stirred and are warming up to back flow reaction
20h, cooling, filters out ball, is washed with dimethoxym ethane, be washed with water and wash, obtain resin；
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, 170 DEG C is warming up to instead
10h is answered, washing is filtered and is obtained resin；
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and in reactor, add 25% sodium hydroxide molten
Liquid 60g, ethanol 80g, stir and are warming up to 50 DEG C；2- chloropyridine 40g streams are added in 500ml reactors, Jing 8h streams are added
Finish, be incubated 50 DEG C afterwards, react 27h, terminate, filter out resin, with washing with alcohol, wash and obtain resin；
Above-mentioned resin is weighed into 100g, 500ml glass reaction kettles are put into, 100g water and 0.96g tetraethylammonium bromides is added, is risen
Temperature to 30 DEG C, by allyl sulfides 52g, add in reactor in the 3h by stream, is warming up to 40 DEG C of reaction 5h afterwards, terminates reaction, Jing
Washing with alcohol, washing obtain resin；
Through its structure of naval stores obtained in above-mentioned reaction it is：
Or：
Configured with tap water 8% sodium chloride solution 500ml is added in 1000ml reactors, then is added thereto to hydroxyl second
Base cellulose 1g and gelatin 2.5g, stir and be warming up to 45 DEG C be uniformly dissolved after, stop stirring it is standby；Claimed with dried beaker
80% divinylbenzene 7.5g and styrene 92.5g are taken, toluene 100g, dibenzoyl peroxide 0.8g, after stirring is added
It is added in 1000ml reactors, stands 10min, unlatching is stirred and adjusted mixing speed, makes oil phase be separated into 0.2～0.7mm
Spherical particle, be warming up to 80 DEG C insulation 3h, after ball solidification after be warming up to 90 DEG C continue reaction 5h；After reaction terminates, filter
Go out cured ball, carrying out washing to ball with dimethoxym ethane makes toluene washes clean, is washed with water and washs to without dimethoxym ethane, obtains
Resin；
When the ball of the solidification of above-mentioned preparation is put in 3h in 105 DEG C of baking ovens, ball water content after being dried is determined, if be less than
Stop drying when 3% and in dry environment, make resin temperature be down to room temperature, otherwise continue to dry up to water content is qualified and done
Resin；
Above-mentioned dried resin is weighed into 50g, is added in dry 500ml reactors, and dichloro is added in reactor
Ethane 200g, acetic anhydride 30g, N- hydroxymethylphthalimide 70g, concentrated sulphuric acid 30g, unlatching are stirred and are warming up to back flow reaction
20h, cooling, filters out ball, is washed with dimethoxym ethane, be washed with water and wash, obtain resin；
Above-mentioned resin is all added in autoclave, 30% sodium hydroxide solution 120g is added, 170 DEG C is warming up to instead
10h is answered, washing is filtered and is obtained resin；
Above-mentioned resin 100g is weighed, is added in 500ml glass reaction kettles, and in reactor, add 25% sodium hydroxide molten
Liquid 60g, ethanol 80g, stir and are warming up to 50 DEG C；2- chloropyridine 40g streams are added in 500ml reactors, Jing 8h streams are added
Finish, be incubated 50 DEG C afterwards, react 27h, terminate, filter out resin, with washing with alcohol, wash and obtain resin；
Above-mentioned resin 100g is taken, is put in 500ml reactors, added 100g water and 0.8g tetraethylammonium bromides, be warming up to 30
DEG C, by expoxy propane 41g, stream is added in reactor in the 3h, is warming up to 40 DEG C of reaction 5h afterwards, is terminated reaction, and Jing ethanol is washed
Wash, washing obtains resin；
Through its structure of naval stores obtained in above-mentioned reaction it is：
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