CN109651573A - Nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound - Google Patents

Nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound Download PDF

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CN109651573A
CN109651573A CN201710945868.2A CN201710945868A CN109651573A CN 109651573 A CN109651573 A CN 109651573A CN 201710945868 A CN201710945868 A CN 201710945868A CN 109651573 A CN109651573 A CN 109651573A
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graphene
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milliliters
ion exchange
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CN109651573B (en
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李亚男
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

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Abstract

The present invention relates to nano inorganic oxide-graphene-ion exchange resin materials of strong basicity tri compound and preparation method thereof, the prior art is mainly solved there are the basic activated group content of strong basic ion exchange resin catalyst is low, and the correspondingly not high problem of activity in catalyst application process.The present invention is by using in terms of the weight percent of resin material gross weight, including following component: (a) 70~85 parts of polymerized monomer；(b) 3~15 parts of comonomer；(c) 0.1~10 part of graphene；(d) 0.1~1 part of nano inorganic oxide component；(e) technical solution of 0.1~10 part of initiator preferably solves the problems, such as this, can be used in the industrial production of strong basicity combination ion exchange resin material catalyst.

Description

Nano inorganic oxide-graphene-ion exchange resin of strong basicity tri compound Material
Technical field
The present invention relates to nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound and Preparation method.
Background technique
Graphene is a kind of novel nano-carbon material, in view of the high intensity of graphene, high conductivity, intensity it is big, can be soft The prominent property such as tough bending, graphene provide wide development space for novel, high performance polymer based composites. Composite material is prepared using graphene and polymer matrix bluk recombination, physical-mechanical properties, the electrical property of material can be obviously improved Matter etc., has broad application prospects.
Nano-oxide due to nano material peculiar property and have excellent performance, existing researcher is into one Step research and utilization nano-oxide such as is doped, coats, being modified at the composite material that can prepare different-shape, becomes new Research hotspot.Hydro-thermal method is the more one kind of research in the synthetic method of nano-oxide, as inorganic oxide solubility forerunner In the closed reaction vessel of body salt in a heated condition, using water as medium, many compounds show difference in reaction system In the physico-chemical property of room temperature, such as solubility increases, compound crystal structure easily makes the transition, the oxide products being recrystallized to give Grain is small and is evenly distributed, purity is high.Using polyethylene glycol as surfactant, oxalic acid cobalt precursor is prepared under hydrothermal conditions Obtain the Co of the higher different-shape of purity3O4, and even grain size (Yang Youping, Huang Kelong, Liu Rensheng etc., Central South University Journal, 2006,37,1103).Pires etc. is with SnCl2·2H2O is soluble precursor salt, is synthesized by microwave-assisted hydro-thermal method SnO powder can obtain the nanometer of different size and form by the method for adjusting hydrothermal synthesis time, temperature and its concentration Crystal (Pires F I, Joanni E, Savu R et al, Material Letters, 2008,62,239).Document CN106340633A, which discloses to report, obtains SnO using the synthetic method of hydro-thermal2/ carbon material and V2O5/ graphene composite wood Material, and SnO is further obtained by the method that ball milling is blended2/ carbon/V2O5/ graphene composite nano material.But above-mentioned technology In have the requirement of stronger hydrophily due to the material that hydro-thermal law system deposits nano-oxide, using liquid glucose or tool Have compared with strongly hydrophilic can graphene oxide, the evenly dispersed of aqueous solution and deposition materials can be promoted, thus obtain stablize it is equal Even suspension reaches preferable deposition effect, and its two different oxide is further passed through after being respectively synthesized preparation Physical mixed molding.Document CN104356258A, which is disclosed, reports the absorption property for using rare-earth element modified dealdehyding resin Method, still, in above-mentioned technology, after needing first to be synthetically prepared sulfonation acidic resins using polymerization technique, then by rare earth element nitre Acid solution is added in molded resin and is modified.Existing commercially available commercial 201 type strong-basicity styrene series anion exchange tree The full exchange capacity of rouge is about 3.4mmol/g.
Summary of the invention
Problem to be solved by this invention first is that the prior art there are strong basic ion exchange resin catalyst alkalinity is living Property group content it is low, and the correspondingly not high problem of activity in catalyst application process provides a kind of new strong basicity ternary Compound nano inorganic oxide-graphene-ion exchange resin material, the resin have basic functional group content height, The strong feature of activity in reaction process.
The second technical problem to be solved by the present invention is to provide the corresponding highly basic of one of one kind and solution technical problem Nano inorganic oxide-graphene-ion exchange resin material preparation method of property tri compound.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: the nanometer of strong basicity tri compound Inorganic oxide-graphene-ion exchange resin material, it is characterized in that, in terms of the parts by weight of resin material gross weight, including Following components:
(a) 70~85 parts of polymerized monomer；
(b) 3~15 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of nano inorganic oxide component；
(e) 0.1~10 part of initiator；
Wherein, the polymerized monomer is selected from at least one of the compound of flowering structure；
The polymerized monomer preferably is selected from p-chloromethyl styrene, 4- (3- chloropropyl) styrene, 4- (3- bromopropyl) benzene second Alkene, 4- (4- chlorobutyl) styrene, 4- (4- brombutyl) styrene, 4- (5- chlorine amyl) styrene or 4- (5- bromine amyl) benzene second At least one of alkene；
Polymerized monomer described in above-mentioned technical proposal is more preferably from p-chloromethyl styrene and 4- (3- chloropropyl) styrene；
The comonomer is selected from at least one of the compound of flowering structure；
The comonomer preferably is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane, two At least one of vinyl benzene；
Comonomer described in above-mentioned technical proposal is more preferably from diallyl benzene and divinylbenzene；The nano inorganic At least one in the nano-oxide of nano-oxide or/and the 4th B metal of the oxide component selected from the second B metal Kind.
In above-mentioned technical proposal, preferred technical solution is that second B metal is selected from zinc.
In above-mentioned technical proposal, preferred technical solution is at least one of the metal of the 4th subgroup in titanium, zirconium Kind.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from the nano-oxide of the second B metal zinc The nano-oxide of zinc oxide and the 4th subgroup Titanium；The molar ratio of zinc oxide and titanium oxide is (1:3)~(3:1), the two There is synergistic effect in terms of the high activity for improving resin material.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from the nano-oxide of the second B metal zinc The molar ratio of the nano-oxide of zinc oxide and the 4th subgroup metal zirconium, zinc oxide and zirconium oxide is (1:3)~(3:1)；The two There is synergistic effect in terms of the high activity for improving resin material.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from receiving for the 4th subgroup metal zirconium and Titanium The molar ratio of rice oxide, zirconium oxide and titanium oxide is (1:3)~(3:1)；The two is in terms of the high activity for improving resin material With synergistic effect.
In above-mentioned technical proposal, the more preferable autoxidation zinc of the nano inorganic oxide component, titanium oxide and zirconium oxide this The composition of three kinds of nano-oxides, the molar ratio of zinc oxide, zirconium oxide and titanium oxide are 1:(0.5~2): (0.5~2), three Kind nano-oxide is used in conjunction with, and has synergistic effect in terms of the high activity for improving resin material.
The initiator is in benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, isopropyl benzene hydroperoxide At least one.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the nanometer of strong basicity tri compound Inorganic oxide-graphene-ion exchange resin material preparation method, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into the aqueous solution that molar concentration is 0.01~5 mol/L A；Wherein the nano inorganic oxide group is selected from the nano-oxide and/or the 4th B metal of the second B metal At least one of corresponding soluble precursor salt of nano-oxide；
(2) solution A is impregnated into graphene, sonic oscillation 1~6 hour under room temperature, it is heavy to be added in high-pressure reactor Shallow lake agent, 100~500 DEG C at a temperature of hydrothermal decomposition 2~24 hours, then Slow cooling, be washed to room temperature, be made nanometer nothing Machine oxide-graphene binary material B；Wherein the precipitating reagent is selected from deionized water, ammonium hydroxide, urea, sodium hydroxide or hydrogen-oxygen Change at least one of potassium.
(3) reagent and additive in polymerization is made into the aqueous solution C that weight percent concentration is 0.3~3%；Wherein, the reagent and additive in polymerization Selected from least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；The dosage of reagent and additive in polymerization is The 5~50% of polymerized monomer weight；
(4) nano inorganic oxide-that will be prepared in the desired amount of polymerized monomer, comonomer, initiator and step (2) Graphene binary material B is mixed into solution D；
(5) by solution D 40~60 DEG C prepolymerization 0.5~2.5 hour；Solution D and solution B are stirred, are warming up to It 55~85 DEG C, reacts 3~10 hours, then heats to 80~95 DEG C, react 3~10 hours curing moldings；After reaction, incline Pour out supernatant liquid, washed, filtering, dry, sieving, the nanometer nothing of the tri compound of 0.35~0.60mm of collection cut size range Machine oxide-graphene-ion exchange resin beads；
(6) sweller for being equivalent to complex microsphere weight 100~200%, 50~150% are added into tri compound microballoon Amination reagent and 50~150% alkali, reacted at 25~40 DEG C about 3~20 hours；After reaction, it is washed, is added Alkali transition, then it is washed to neutrality, obtain nano inorganic oxide-graphene-amberlite of the strong basicity tri compound Rouge material.
Wherein the sweller is selected from methylene chloride, 1,2- dichloroethanes, chloroform, N,N-dimethylformamide, two At least one of methyl sulfoxide or tetrahydrofuran；The amination reagent is selected from front three amine salt, triethylamine salt, diethylamine salt or three At least one of butylamine salt；The alkali is selected from least one of sodium hydroxide, potassium hydroxide or sodium bicarbonate.
In above-mentioned technical proposal, it is preferable that the precipitating reagent is selected from least one of water or sodium hydroxide.
In above-mentioned technical proposal, it is preferable that the reagent and additive in polymerization is selected from least one of polyvinyl alcohol or gelatin.
In above-mentioned technical proposal, it is preferable that the sweller is selected from least one of methylene chloride or tetrahydrofuran.
In above-mentioned technical proposal, it is preferable that the amination reagent is selected from least one of front three amine salt or triethylamine salt.
The single-layer graphene and multi-layer graphene of use in the present invention can by epitaxial growth method, chemical vapour deposition technique, The methods of graphene oxide reduction method is prepared.This has been graphene preparation technology well known in the art, document CN201210561249.0 discloses report.
Ion exchange resin cross-linked scaffold involved in the present invention is polystyrene, synthesizes copolymerization skeleton by polymerization reaction Afterwards, functional group quaternary ammonium group is further introduced by aminating reaction.Specifically, inorganic oxide soluble precursor salt is direct It is generated by hydro-thermal method and nano-inorganic substance and loads to graphene surface, obtain that granularity is smaller and the nano inorganic oxidation that is uniformly dispersed Object-graphene binary complex.When the nano inorganic oxide-graphene binary complex participates in polymerization reaction, make nanometer Inorganic oxide-graphene binary complex and polymer carbon are grafted, and finally obtain the nano inorganic oxidation of tri compound Object-graphene-ion exchange resin beads.Functional group quaternary ammonium group is introduced by aminating reaction, it is multiple to obtain strong basicity ternary Nano inorganic oxide-graphene-ion exchange resin material of conjunction.
Using technical solution of the present invention, nanometer is dispersed by nano inorganic oxide load using the method for hydrothermal deposition Material graphene surface, and the graphene that deposited nano-oxide is applied in polymerization reaction, realize new strong basicity It is multiple to solve strong basicity graphene for the nano inorganic oxide of tri compound-graphene-ion exchange resin material preparation It is low to close the basic activated group content of ion-exchange resin catalyst, and correspondingly activity not high is asked in catalyst application process Topic.Nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound in the present invention has alkali Sexual function group content is high, and the strong feature of activity, achieves preferable technical effect in actual application in reaction process.
The nano inorganic oxide of strong basicity tri compound of the invention-graphene-ion exchange resin material alkali Property group content measuring method it is as follows: use hydrochloric acid standard solution titration, take 2.5 grams of resin material, 0.1 mol/L is added 100 milliliters of hydrochloric acid standard solution, 40 DEG C at a temperature of heating water bath 2 hours after it is cooling.25 milliliters of soak are taken, is added 50 2~3 drop instructions phenolphthalein solutions are added dropwise in ml deionized water.It is titrated with the standard solution of sodium hydroxide of 0.1 mol/L, records hydrogen-oxygen Change sodium standard solution volume V1Milliliter.Separately take 1 gram of resin material, 105 DEG C at a temperature of drying to constant weight, record quality at this time m1Gram.
The water content calculation formula of resin is
The basic group content calculation formula of resin surface is
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
The 50 ml deionized water solution for having dissolved 0.745 gram of zinc nitrate hexahydrate are poured into 2.5 grams of multi-layer graphenes Water heating kettle is poured into (0.05 mol/L of molar concentration), stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, and 160 It is kept for 24 hours at DEG C, is cooled to room temperature, is washed with deionized water, poured into 250 milliliters of three-necked flasks, be added 80.6 grams to chlorine Methyl styrene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress pre-polymerization in 2 hours at 60 DEG C It closes.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Mixing speed is adjusted, while being gradually warming up to It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, incline Supernatant liquid is poured out, is washed with hot water, is then filtered, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon A within the scope of 0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon A and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Materials A.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin materials As is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide-graphite of strong basicity tri compound Alkene-ion exchange resin material A.
[embodiment 2]
It takes 0.851 gram of butyl titanate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), impregnates Into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 small in hydro-thermal furnace at 160 DEG C When, it is cooled to room temperature, is washed with deionized water, obtain nano-titanium oxide-graphene binary composite sample.At 250 milliliters three mouthfuls In flask, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, in 60 Progress prepolymerization in 2 hours is stirred at DEG C.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjusting is stirred Speed is mixed, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, instead It answers 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying, mistake in baking oven Sieve, tri compound microballoon B of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon B and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material B.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material B is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide-graphite of strong basicity tri compound Alkene-ion exchange resin material B.
[embodiment 3]
Poured into 2.5 grams of multi-layer graphenes dissolved 0.805 gram of zirconium oxychloride octahydrate deionized water solution it is (mole dense Spend 0.05 mol/L), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, keeps at 160 DEG C It 24 hours, is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethylbenzene second Alkene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.It is added It has been dissolved with the 150 ml deionized water solution of 1.5 grams of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, instead It answers 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, upper layer is poured out Liquid is washed with hot water, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, collection cut size is within the scope of 0.35-0.60mm Tri compound microballoon C.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon C and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material C.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material Cs is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zircite-graphite of strong basicity tri compound Alkene-ion exchange resin material C.
[embodiment 4]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.186 gram of zinc nitrate hexahydrate and 0.638 gram of butyl titanate 50 ml deionized water solution (molar concentration is respectively 0.0125 mol/L and 0.0375 mol/L, molar concentration rate 1: 3), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound of the collection cut size within the scope of 0.35-0.60mm Microballoon D.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon D and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material D.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material D is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium-graphene-ion exchange resin material D.
[embodiment 5]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.425 gram of butyl titanate and 0.372 gram of zinc nitrate hexahydrate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, molar concentration rate 2:2), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound microballoon of the collection cut size within the scope of 0.35-0.60mm E。
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon E and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material E.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material E is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium-graphene-ion exchange resin material E.
[embodiment 6]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.558 gram of zinc nitrate hexahydrate and 0.213 gram of butyl titanate 50 ml deionized water solution (molar concentration is respectively 0.0375 mol/L and 0.0125 mol/L, molar concentration rate 3: 1), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound of the collection cut size within the scope of 0.35-0.60mm Microballoon F.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon F and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material F.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material F is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium-graphene-ion exchange resin material F.
[embodiment 7]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.186 gram of zinc nitrate hexahydrate and 0.604 gram of zirconium oxychloride octahydrate 50 ml deionized water solution (molar concentration is respectively 0.0125 mol/L and 0.0375 mol/L, and molar concentration rate is 1:3), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, was kept for 24 hours at 160 DEG C, cold But it to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 grams Divinylbenzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 150 ml deionized water solution of 1.5 grams of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours； It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, supernatant liquid is poured out, uses Hot water washing, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, and ternary of the collection cut size within the scope of 0.35-0.60mm is answered Close microballoon G.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon G and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material G.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material G is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material G.
[embodiment 8]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.403 gram of zirconium oxychloride octahydrate and 0.372 gram of zinc nitrate hexahydrate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, molar concentration rate 2: 2), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound of the collection cut size within the scope of 0.35-0.60mm Microballoon H.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon H and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material H.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material H is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material H.
[embodiment 9]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.558 gram of zinc nitrate hexahydrate and 0.201 gram of zirconium oxychloride octahydrate 50 ml deionized water solution (molar concentration is respectively 0.0375 mol/L and 0.0125 mol/L, and molar concentration rate is 3:1), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, was kept for 24 hours at 160 DEG C, cold But it to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 grams Divinylbenzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 150 ml deionized water solution of 1.5 grams of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours； It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, supernatant liquid is poured out, uses Hot water washing, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, and ternary of the collection cut size within the scope of 0.35-0.60mm is answered Close microballoon I.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon I and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material I.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material I is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material I.
[embodiment 10]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of butyl titanate and 0.604 gram of zirconium oxychloride octahydrate 50 ml deionized water solution (molar concentration is respectively 0.0125 mol/L and 0.0375 mol/L, molar concentration rate 1: 3), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound of the collection cut size within the scope of 0.35-0.60mm Microballoon J.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon J and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material J.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material J is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material J.
[embodiment 11]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.403 gram of zirconium oxychloride octahydrate and 0.425 gram of butyl titanate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, molar concentration rate 2:2), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound microballoon of the collection cut size within the scope of 0.35-0.60mm K。
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon K and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material K.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material K is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material K.
[embodiment 12]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.638 gram of butyl titanate and 0.201 gram of zirconium oxychloride octahydrate 50 ml deionized water solution (molar concentration is respectively 0.0375 mol/L and 0.0125 mol/L, molar concentration rate 3: 1), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, tri compound of the collection cut size within the scope of 0.35-0.60mm Microballoon L.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon L and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material L.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material L is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material L.
[embodiment 13]
Poured into 2.5 grams of multi-layer graphenes dissolved 0.149 gram of zinc nitrate hexahydrate, 0.340 gram of butyl titanate and (molar concentration is respectively 0.01 mol/L, 0.02 mol/L to 50 ml deionized water solution of 0.322 gram of zirconium oxychloride octahydrate With 0.02 mol/L, molar concentration rate 1:2:2), water heating kettle is poured into stirring, and water heating kettle was placed on water through sonic oscillation 1 hour It in hot stove, is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, poured into 250 milliliters of three-necked flasks, be added It is small to stir 2 at 60 DEG C for 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator Shi Jinhang prepolymerization.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Mixing speed is adjusted, simultaneously 80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction After, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size exists Tri compound microballoon M within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon M and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material M.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material M is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium/zirconium oxide-graphene-ion exchange resin material M.
[embodiment 14]
Poured into 2.5 grams of multi-layer graphenes dissolved 0.298 gram of zinc nitrate hexahydrate, 0.170 gram of butyl titanate and (molar concentration is respectively 0.02 mol/L, 0.01 mol/L to 50 ml deionized water solution of 0.322 gram of zirconium oxychloride octahydrate With 0.02 mol/L, molar concentration rate 2:1:2), water heating kettle is poured into stirring, and water heating kettle was placed on water through sonic oscillation 1 hour It in hot stove, is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, poured into 250 milliliters of three-necked flasks, be added It is small to stir 2 at 60 DEG C for 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator Shi Jinhang prepolymerization.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Mixing speed is adjusted, simultaneously 80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction After, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size exists Tri compound microballoon N within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon N and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material N.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material N is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium/zirconium oxide-graphene-ion exchange resin material N.
[embodiment 15]
Poured into 2.5 grams of multi-layer graphenes dissolved 0.298 gram of zinc nitrate hexahydrate, 0.340 gram of butyl titanate and (molar concentration is respectively 0.02 mol/L, 0.02 mol/L to 50 ml deionized water solution of 0.161 gram of zirconium oxychloride octahydrate With 0.01 mol/L, molar concentration rate 2:2:1), water heating kettle is poured into stirring, and water heating kettle was placed on water through sonic oscillation 1 hour It in hot stove, is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, poured into 250 milliliters of three-necked flasks, be added It is small to stir 2 at 60 DEG C for 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator Shi Jinhang prepolymerization.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Mixing speed is adjusted, simultaneously 80 DEG C are gradually warming up to, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction After, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size exists Tri compound microballoon O within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon O and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material O.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material O is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium/zirconium oxide-graphene-ion exchange resin material O.
[embodiment 16]
Poured into 2.5 grams of multi-layer graphenes dissolved 0.248 gram of zinc nitrate hexahydrate, 0.284 gram of butyl titanate and (molar concentration is respectively 0.0167 mol/L, 0.0167 rubs 50 ml deionized water solution of 0.269 gram of zirconium oxychloride octahydrate You/liter and 0.0167 mol/L, molar concentration rate 1:1:1), stir pour into water heating kettle, water heating kettle was through sonic oscillation 1 hour It is placed in hydro-thermal furnace, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, pour into 250 milliliters of three mouthfuls of burnings In bottle, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, in 60 DEG C Lower stirring progress prepolymerization in 2 hours.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjust stirring Speed, while 80 DEG C are gradually warming up to, it reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reaction 6 Hour.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, is sieved, receive Collect tri compound microballoon P of the partial size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon P and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material P.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material P is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium/zirconium oxide-graphene-ion exchange resin material P.
[embodiment 17]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.186 gram of zinc nitrate hexahydrate and 0.638 gram of butyl titanate 50 ml deionized water solution (molar concentration is respectively 0.0125 mol/L and 0.0375 mol/L, molar concentration rate 1: 3), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, cooling It to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes and 4- (3- chlorine are added Propyl) styrene mixture (weight ratio between the two be 1:1), 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide Initiator stirs progress prepolymerization in 2 hours at 60 DEG C.150 ml deionized waters for being dissolved with 1.5 grams of polyvinyl alcohol are added Solution.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, finally rises Temperature is reacted 6 hours to 98 DEG C.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 in baking oven DEG C drying, sieving, tri compound microballoon D2 of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon D2 and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material D2.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material D2 is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Titanium-graphene-ion exchange resin material D2.
[embodiment 18]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.186 gram of zinc nitrate hexahydrate and 0.604 gram of zirconium oxychloride octahydrate 50 ml deionized water solution (molar concentration is respectively 0.0125 mol/L and 0.0375 mol/L, and molar concentration rate is 1:3), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, was kept for 24 hours at 160 DEG C, cold But it to room temperature, is washed with deionized water, pours into 250 milliliters of three-necked flasks, be added 80.6 grams of p-chloromethyl styrenes, 3.5 grams The mixture (weight ratio between the two is 1:1) of divinylbenzene and diallyl benzene, 0.1 gram of benzoyl peroxide causes Progress prepolymerization in 2 hours is stirred in agent at 60 DEG C.150 ml deionized waters that addition has been dissolved with 1.5 grams of polyvinyl alcohol are molten Liquid.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, finally heats up To 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into baking oven 80 DEG C Drying, sieving, tri compound microballoon G2 of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon G2 and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material G2.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material G2 is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano zine oxide/oxidation of strong basicity tri compound Zirconium-graphene-ion exchange resin material G2.
[embodiment 19]
It takes 0.851 gram of butyl titanate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), impregnates Into 2.5 grams of single-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 small in hydro-thermal furnace at 160 DEG C When, it is cooled to room temperature, is washed with deionized water, obtain nano-titanium oxide-graphene binary composite sample.At 250 milliliters three mouthfuls In flask, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, in 60 Progress prepolymerization in 2 hours is stirred at DEG C.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjusting is stirred Speed is mixed, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, instead It answers 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying, mistake in baking oven Sieve, tri compound microballoon B2 of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon B2 and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material B2.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material B2 is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide-graphite of strong basicity tri compound Alkene-ion exchange resin material B2.
[embodiment 20]
It takes 0.851 gram of butyl titanate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), impregnates Into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 small in hydro-thermal furnace at 160 DEG C When, it is cooled to room temperature, is washed with deionized water, obtain nano-titanium oxide-graphene binary composite sample.At 250 milliliters three mouthfuls In flask, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of azodiisobutyronitrile initiator is added, in 60 Progress prepolymerization in 2 hours is stirred at DEG C.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjusting is stirred Speed is mixed, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, instead It answers 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying, mistake in baking oven Sieve, tri compound microballoon B3 of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of tri compound microballoon B3 and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, tri compound microballoon is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get trielement ion exchanger resin Material B3.
Last handling process is as follows: 50 milliliters of above-mentioned trielement ion exchanger resin material B3 is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get nano-titanium oxide-graphite of strong basicity tri compound Alkene-ion exchange resin material B3.
[embodiment 21]
Evaluate the ion exchange resin material A~P, D2, G2, B2, B3 of strong basicity tri compound obtained by [Examples 1 to 2 0] Water content and basic group content, the results are shown in Table 1.
[comparative example 1]
In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of multilayers are added Graphene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams 150 ml deionized water solution of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It rises again Temperature is reacted 5 hours to 90 DEG C, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, uses hot water Washing, is then filtered, and is put into 80 DEG C of drying in baking oven, is sieved, binary of the collection cut size within the scope of 0.35-0.60mm is compound micro- Ball Q.
In 250 milliliters of three-necked flasks, 30 grams of binary complex microsphere Q and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, binary complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get binary combination ion exchange resin Material Q.
Last handling process is as follows: 50 milliliters of above-mentioned binary combination ion exchange resin material Q is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, and the moisture graphene-ion exchange compound to get strong basicity binary is dried at 25 DEG C of room temperature Resin material Q.
With [embodiment 21], the water content and basic group content of ion exchange resin material Q are evaluated, the results are shown in Table 1.
[comparative example 2]
It takes 0.877 gram of stannic chloride pentahydrate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), soaks For stain into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 at 160 DEG C in hydro-thermal furnace Hour, it is cooled to room temperature, is washed with deionized water, obtain nano tin dioxide-graphene binary composite sample.250 milliliters three mouthfuls In flask, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes are added, 2.5 grams of nano tin dioxides-graphene binary is answered Sample and 0.1 gram of benzoyl peroxide initiator are closed, progress prepolymerization in 2 hours is stirred at 60 DEG C.Addition has been dissolved with 1.5 grams 150 ml deionized water solution of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It rises again Temperature is reacted 5 hours to 90 DEG C, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, uses hot water Washing, is then filtered, and is put into 80 DEG C of drying in baking oven, is sieved, binary of the collection cut size within the scope of 0.35-0.60mm is compound micro- Ball R.
In 250 milliliters of three-necked flasks, 30 grams of binary complex microsphere R and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, binary complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get binary combination ion exchange resin Material R.
Last handling process is as follows: 50 milliliters of above-mentioned binary combination ion exchange resin material R is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get the nano oxidized tin-graphite of strong basicity tri compound Alkene-ion exchange resin material R.
With [embodiment 21], the water content and basic group content of ion exchange resin material R are evaluated, the results are shown in Table 1.
[comparative example 3]
0.676 gram of Iron(III) chloride hexahydrate is taken to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), It is impregnated into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, is kept in hydro-thermal furnace at 160 DEG C It 24 hours, is cooled to room temperature, is washed with deionized water, obtain nano iron oxide-graphene binary composite sample.250 milliliter three In mouth flask, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of nano iron oxides-graphene binary are added Composite sample and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, be sieved, binary of the collection cut size within the scope of 0.35-0.60mm is compound Microballoon S.
In 250 milliliters of three-necked flasks, 30 grams of binary complex microsphere S and 50 milliliters of dichloroethanes are added, by bath temperature 30 DEG C are adjusted to, binary complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides and quality point are added Number is 130 milliliters of sodium hydroxide solution of 20%, is reacted about 8 hours at 30 DEG C or so.After reaction, it is gradually diluted with water to When specific gravity is equal to 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get binary combination ion exchange resin Material S.
Last handling process is as follows: 50 milliliters of above-mentioned binary combination ion exchange resin material S is taken, with 200 milliliters of methanol It is washed after immersion with 700 ml deionized waters.Be then charged into the glass column with husky core, resin be washed with deionized, go from Sub- water flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin, flow velocity 2 are washed with the HCl solution of 0.75 mol/L Ml/min, processing time are 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mole/ The NaOH solution risen washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then it is washed with deionized Resin is neutrality up to eluate, dries moisture at 25 DEG C of room temperature to get the nano oxidized iron-graphite of strong basicity tri compound Alkene-ion exchange resin material S.
With [embodiment 21], the water content and basic group content of ion exchange resin material S are evaluated, the results are shown in Table 1.
Table 1

Claims (8)

1. nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound, it is characterized in that, with resin The parts by weight meter of material gross weight, including following components:
(a) 70~85 parts of polymerized monomer；
(b) 3~15 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of nano inorganic oxide component；
(e) 0.1~10 part of initiator；
Wherein, the polymerized monomer is selected from at least one of the compound of flowering structure；
The comonomer is selected from at least one of the compound of flowering structure；
The graphene is selected from least one of single-layer graphene or multi-layer graphene；
The nano inorganic oxide group is selected from the nano-oxide of the second B metal or/and the nanometer of the 4th B metal At least one of oxide；
The initiator in benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, isopropyl benzene hydroperoxide extremely Few one kind.
2. nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound according to claim 1 Material, it is characterised in that second B metal is selected from zinc.
3. nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound according to claim 1 Material, it is characterised in that the metal of the 4th subgroup is selected from least one of titanium, zirconium.
4. a kind of nano inorganic oxide-graphene-using any one strong basicity tri compound in claims 1 to 3 from The preparation method of sub-exchange resin material, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into the water solution A that molar concentration is 0.01~5 mol/L；Its Described in nano inorganic oxide group be selected from the nano-oxide of the second B metal and/or the nanometer of the 4th B metal At least one of corresponding soluble precursor salt of oxide；
(2) solution A being impregnated into graphene, sonic oscillation 1~6 hour, is added precipitating reagent in high-pressure reactor under room temperature, 100~500 DEG C at a temperature of sealing thermal insulation 2~24 hours, then Slow cooling, be washed to room temperature, be made nano inorganic oxygen Compound-graphene binary material B；Wherein the precipitating reagent is selected from deionized water, ammonium hydroxide, urea, sodium hydroxide or potassium hydroxide At least one of.
(3) reagent and additive in polymerization is made into the aqueous solution C that weight percent concentration is 0.3~3%；Wherein, the reagent and additive in polymerization is selected from At least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；The dosage of reagent and additive in polymerization is polymerization The 5~50% of monomer weight；
(4) nano inorganic oxide-graphite that will be prepared in the desired amount of polymerized monomer, comonomer, initiator and step (2) Alkene binary material B is mixed into solution D；
(5) by solution D 40~60 DEG C prepolymerization 0.5~2.5 hour；Solution D and solution C are stirred, it is warming up to 55~ It 85 DEG C, reacts 3~10 hours, then heats to 80~95 DEG C, react 3~10 hours curing moldings；After reaction, it is poured out Supernatant liquid, washed, filtering, dry, sieving, the nano inorganic oxygen of the tri compound of 0.35~0.60mm of collection cut size range Compound-graphene-ion exchange resin beads；
(6) amine of the sweller, 50~150% that are equivalent to complex microsphere weight 100~200% is added into tri compound microballoon The alkali for changing reagent and 50~150%, reacts about 3~20 hours at 25~40 DEG C；After reaction, it is washed, alkali is added and turns Type, then it is washed to neutrality, obtain nano inorganic oxide-graphene-ion exchange resin material of the strong basicity tri compound Material.
5. nano inorganic oxide-graphene-ion exchange resin of strong basicity tri compound according to claim 4 The preparation method of material, it is characterised in that the sweller is selected from methylene chloride, 1,2- dichloroethanes, chloroform, N, N- bis- At least one of methylformamide, dimethyl sulfoxide or tetrahydrofuran.
6. nano inorganic oxide-graphene-ion exchange resin of strong basicity tri compound according to claim 4 The preparation method of material, it is characterised in that the amination reagent is selected from front three amine salt, triethylamine salt, diethylamine salt or tri-n-butylamine salt At least one of；The alkali is selected from least one of sodium hydroxide, potassium hydroxide or sodium bicarbonate.
7. nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound according to claim 4 Preparation method, it is characterised in that the precipitating reagent be selected from least one of water or sodium hydroxide.
8. nano inorganic oxide-graphene-ion exchange resin material of strong basicity tri compound according to claim 4 Preparation method, it is characterised in that the reagent and additive in polymerization be selected from least one of polyvinyl alcohol or gelatin；The sweller choosing From at least one of methylene chloride or tetrahydrofuran；The amination reagent in front three amine salt or triethylamine salt at least one Kind.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027141A2 (en) * 2008-09-05 2010-03-11 성균관대학교 산학협력단 Novel fullerene derivative and preparation method thereof
CN104558359A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of strong basic graphene composite resin material
CN104558360A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Strong-alkalinity composite ion exchange resin material and preparation method thereof
CN104926975A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Strong alkaline composite resin material and preparation method thereof
CN109651552B (en) * 2017-10-11 2021-03-30 中国石油化工股份有限公司 Strong alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027141A2 (en) * 2008-09-05 2010-03-11 성균관대학교 산학협력단 Novel fullerene derivative and preparation method thereof
CN104558359A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of strong basic graphene composite resin material
CN104558360A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Strong-alkalinity composite ion exchange resin material and preparation method thereof
CN104926975A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Strong alkaline composite resin material and preparation method thereof
CN109651552B (en) * 2017-10-11 2021-03-30 中国石油化工股份有限公司 Strong alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material

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