CN109651554A - Nano inorganic oxide-carbon nanotubes-ion exchange resin material of strong basicity tri compound - Google Patents

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

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CN109651554A
CN109651554A CN201710945980.6A CN201710945980A CN109651554A CN 109651554 A CN109651554 A CN 109651554A CN 201710945980 A CN201710945980 A CN 201710945980A CN 109651554 A CN109651554 A CN 109651554A
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carbon nanotubes
hours
inorganic oxide
milliliters
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CN109651554B (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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    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2289—Oxides; Hydroxides of metals of cobalt

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The present invention relates to nano inorganic oxide-carbon nanotubes-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) 70~90 parts of polymerized monomer；(b) 5~15 parts of comonomer；(c) 0.1~10 part of carbon nanotubes；(d) 0.1~10 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-carbon nanotubes-amberlite of strong basicity tri compound Rouge material
Technical field
The present invention relates to nano inorganic oxide-carbon nanotubes-ion exchange resin materials of strong basicity tri compound And preparation method thereof.
Background technique
Carbon nanotubes is as a kind of novel nano material, due to its unique hollow structure and nano-scale, Yi Jiqi The features such as high-specific surface area, high conductivity, makes it have potential value in fields such as composite material enhancing, catalyst, due to Its high surface area and be widely used in catalyst field.Composite material is prepared using carbon nanotubes and polymer matrix bluk recombination, Physical-mechanical properties, the electrical properties etc. of material can be obviously improved, are had 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 CN105006376A, which discloses to report, obtains NiO/CNTs composite material using the synthetic method of hydro-thermal and chemical vapor deposition, Carbon nanotubes is grown in spherical structure nano NiO surface in situ.But it needs in addition to use chemical vapor deposition in above-mentioned technology Method combines closely NiO and carbon nanotubes, cannot a step realize NiO/CNTs nano material preparation.Document CN104356258A discloses the method for reporting the absorption property using rare-earth element modified dealdehyding resin, still, above-mentioned skill In art, after needing first to be synthetically prepared sulfonation acidic resins using polymerization technique, then rare earth element nitric acid solution is added to and is had become It is modified in the resin of type.The full exchange capacity of existing commercially available commercial 201 type strong-basicity styrene series anion exchange resin is about For 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-carbon nanotubes-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-carbon nanotubes-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-carbon nanotubes-ion exchange resin material, it is characterized in that, in terms of the parts by weight of resin material gross weight, packet Include following components:
(a) 70~85 parts of polymerized monomer；
(b) 3~15 parts of comonomer；
(c) 0.1~10 part of carbon nanotubes；
(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；
N=0,1,2 ... ..., X=Cl, Br, I
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) benzene second Alkene；
The comonomer is selected from at least one of the compound of flowering structure；
The comonomer preferably is selected from divinylbenzene, divinyl phenylmethane, ethyleneglycol dimethyacrylate, two At least one of propenylbenzene；
Comonomer described in above-mentioned technical proposal is more preferably from diallyl benzene and divinylbenzene；The nano inorganic In the nano-oxide of nano-oxide or/and the 8th race's Ferrious material of the oxide component selected from the first B metal at least It is a kind of.
In above-mentioned technical proposal, preferred technical solution is that first B metal is selected from copper.
In above-mentioned technical proposal, preferred technical solution is at least one of the 8th race's Ferrious material in iron, cobalt Kind.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from the nano-oxide of the first B metal copper The nano-oxide of copper oxide and the 8th race's Ferrious material iron；The molar ratio of copper oxide and iron oxide be (1:3)~(3:1), two Person has 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 first B metal copper The molar ratio of the nano-oxide of copper oxide and the 8th race's Ferrious material cobalt, copper oxide and cobalt oxide is (1:3)~(3:1)；Two Person has 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 8th race's Ferrious material iron and metallic cobalt The molar ratio of nano-oxide, iron oxide and cobalt oxide is (1:3)~(3:1)；The two is in the high activity side for improving resin material Face has synergistic effect.
In above-mentioned technical proposal, the more preferable autoxidation copper of the nano inorganic oxide component, iron oxide and cobalt oxide this The composition of three kinds of nano-oxides, the molar ratio of copper oxide, iron oxide and cobalt 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-carbon nanotubes-ion exchange resin material preparation method, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into molar concentration is the water-soluble of 0.01~3 mol/L Liquid A；Wherein the nano inorganic oxide group is selected from the nano-oxide and/or the 8th race's iron series gold of the first B metal At least one of corresponding soluble precursor salt of the nano-oxide of category；
(2) solution A is impregnated into carbon nanotubes, sonic oscillation 1~4 hour, is added in high-pressure reactor under room temperature Precipitating reagent, 100~500 DEG C at a temperature of hydrothermal decomposition 2~24 hours, then Slow cooling, be washed to room temperature, be made nanometer Inorganic oxide-carbon nanotubes binary material B；Wherein the precipitating reagent be selected from deionized water, ammonium hydroxide, urea, sodium hydroxide or At least one of sodium bicarbonate.
(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) Carbon nanotubes 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-carbon nanotubes-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-carbon nanotubes-ion exchange of the strong basicity tri compound Resin 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 carbon nanotubes of use in the present invention is selected from hydroxylating single-walled carbon nanotube, carboxylated dual openings multi-wall carbon nano-tube Pipe or hydroxylated multi-walled carbon nanotubes, this is the carbon nanotube using the special construction of different function scheme preparation.
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 Generated and nano-inorganic substance particle clusters and loaded at the tube wall and nozzle of carbon nanotubes by hydro-thermal method, obtain granularity it is smaller and Be uniformly dispersed nano inorganic oxide-carbon nanotubes binary complex.The nano inorganic oxide-carbon nanotubes binary is compound When object participates in polymerization reaction, it is grafted nano inorganic oxide-carbon nanotubes binary complex and polymer carbon, final To nano inorganic oxide-carbon nanotubes-ion exchange resin beads of tri compound.Function base is introduced by aminating reaction Group's quaternary ammonium group, obtains nano inorganic oxide-carbon nanotubes-ion exchange resin material of strong basicity tri compound.
Using technical solution of the present invention, nanometer is dispersed by nano inorganic oxide load using the method for hydrothermal deposition At the tube wall and nozzle of material nano carbon pipe, and the carbon nanotubes that deposited nano-oxide is applied in polymerization reaction, it is real Nano inorganic oxide-carbon nanotubes-ion exchange resin material preparation of new strong basicity tri compound is showed, has solved Strong basicity graphene combination ion exchange resin catalyst basic activated group content is low, and correspondingly applies in catalyst The not high problem of activity in journey.Nano inorganic oxide-carbon nanotubes of strong basicity tri compound in the present invention-ion is handed over Resin material is changed, has basic functional group content high, the strong feature of activity, obtains in actual application in reaction process Preferable technical effect.
Nano inorganic oxide-carbon nanotubes-ion exchange resin material of strong basicity tri compound of the invention Basic group content assaying method is as follows: use hydrochloric acid standard solution titration, take 2.5 grams of resin material, be added 0.1 mole/ 100 milliliters of hydrochloric acid standard solution risen, 40 DEG C at a temperature of heating water bath 2 hours after it is cooling.25 milliliters of soak are taken, is added 2~3 drop instructions phenolphthalein solutions are added dropwise in 50 ml deionized waters.It is titrated with the standard solution of sodium hydroxide of 0.1 mol/L, records hydrogen Aoxidize sodium standard solution volume V1Milliliter.Separately take 1 gram of resin material, 105 DEG C at a temperature of drying to constant weight, record at this time Quality 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]
50 millis for having dissolved 0.426 gram of Copper dichloride dihydrate are poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes It rises deionized water solution (0.05 mol/L of molar concentration), water heating kettle is poured into stirring, and water heating kettle is through 1 hour postposition of sonic oscillation In hydro-thermal furnace, 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, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, is stirred at 60 DEG C Mix 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 Degree, 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 A 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 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 and receives to get the nano cupric oxide-of strong basicity tri compound Rice carbon pipe-ion exchange resin material A.
[embodiment 2]
It takes 0.595 gram of cobalt chloride hexahydrate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), soaks For stain into 2.5 grams of carboxylated dual openings multi-wall carbon nano-tube pipe powders, water heating kettle is poured into stirring, and sonic oscillation 1 hour, in hydro-thermal furnace It is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, obtain nanometer cobalt oxide-compound sample of carbon nanotubes binary Product.In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of peroxidating is added Benzoyl initiator stirs progress prepolymerization in 2 hours at 60 DEG C.It is added and has been dissolved with 150 milliliters of 1.5 grams of polyvinyl alcohol and goes Deionized water 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, 98 DEG C are finally warming up to, is reacted 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into baking 80 DEG C of drying in case, sieving, 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 and receives to get the nanometer cobalt oxide-of strong basicity tri compound Rice carbon pipe-ion exchange resin material B.
[embodiment 3]
Poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes dissolved 0.676 gram of ferric chloride hexahydrate go from Water heating kettle is poured into sub- aqueous solution (0.05 mol/L of molar concentration), stirring, and water heating kettle was placed on hydro-thermal through sonic oscillation 1 hour It in furnace, 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 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator, stir 2 at 60 DEG C Hour carries out prepolymerization.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Mixing speed is adjusted, It is gradually warming up to 80 DEG C simultaneously, 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 is small When.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, collect Tri compound microballoon C 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 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 iron oxide-nanometer of strong basicity tri compound Carbon pipe-ion exchange resin material C.
[embodiment 4]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.107 gram of Copper dichloride dihydrate and 0.446 Gram cobalt chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0125 mol/L and 0.0375 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon D within the scope of 0.60mm.
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 cupric oxide/oxygen of strong basicity tri compound Change cobalt-carbon nanotubes-ion exchange resin material D.
[embodiment 5]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.297 gram of cobalt chloride hexahydrate and 0.213 Gram Copper dichloride dihydrate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, Molar concentration rate is 2:2), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, protects at 160 DEG C It holds 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 chloromethyl Styrene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C. 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 80 DEG C, it 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, topple over Supernatant liquid out 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 in 0.35-0.60mm Tri compound microballoon E in range.
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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get trielement ion and sets Rouge 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt-carbon nanotubes-ion exchange resin material E.
[embodiment 6]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.320 gram of Copper dichloride dihydrate and 0.149 Gram cobalt chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0375 mol/L and 0.0125 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon F within the scope of 0.60mm.
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 cupric oxide/oxygen of strong basicity tri compound Change cobalt-carbon nanotubes-ion exchange resin material F.
[embodiment 7]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.107 gram of Copper dichloride dihydrate and 0.507 Gram ferric chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0125 mol/L and 0.0375 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon G within the scope of 0.60mm.
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 cupric oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material G.
[embodiment 8]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.338 gram of ferric chloride hexahydrate and 0.213 Gram Copper dichloride dihydrate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, Molar concentration rate is 2:2), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, protects at 160 DEG C It holds 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 chloromethyl Styrene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C. 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 80 DEG C, it 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, topple over Supernatant liquid out 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 in 0.35-0.60mm Tri compound microballoon H in range.
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 cupric oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material H.
[embodiment 9]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.320 gram of Copper dichloride dihydrate and 0.169 Gram ferric chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0375 mol/L and 0.0125 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon I within the scope of 0.60mm.
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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get trielement ion and sets Rouge 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 cupric oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material I.
[embodiment 10]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.149 gram of cobalt chloride hexahydrate and 0.507 Gram ferric chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0125 mol/L and 0.0375 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon J within the scope of 0.60mm.
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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get trielement ion and sets Rouge 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 nanometer cobalt oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material J.
[embodiment 11]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.338 gram of ferric chloride hexahydrate and 0.297 Gram cobalt chloride hexahydrate 50 ml deionized water solution (molar concentration is respectively 0.025 mol/L and 0.025 mol/L, Molar concentration rate is 2:2), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, protects at 160 DEG C It holds 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 chloromethyl Styrene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C. 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 80 DEG C, it 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, topple over Supernatant liquid out 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 in 0.35-0.60mm Tri compound microballoon K in range.
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 nanometer cobalt oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material K.
[embodiment 12]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.446 gram of cobalt chloride hexahydrate and 0.169 Gram ferric chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0375 mol/L and 0.0125 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane Base 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 gradually being heated up To 80 DEG C, react 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, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Tri compound microballoon L within the scope of 0.60mm.
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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get trielement ion and sets Rouge 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 nanometer cobalt oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material L.
[embodiment 13]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.085 gram of Copper dichloride dihydrate, 0.238 (molar concentration is respectively 0.01 to rub to 50 ml deionized water solution of gram cobalt chloride hexahydrate and 0.270 gram of ferric chloride hexahydrate You/liter, 0.02 mol/L and 0.02 mol/L, molar concentration rate 1:2:2), water heating kettle is poured into stirring, and water heating kettle is through super It is placed in hydro-thermal furnace within sound oscillation 1 hour, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, pour into In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide is added Initiator stirs progress prepolymerization in 2 hours at 60 DEG C.150 milliliters of deionizations for being dissolved with 1.5 grams of polyvinyl alcohol are added Aqueous 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 98 DEG C are warming up to, is reacted 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into baking oven 80 DEG C of drying, sieving, tri compound microballoon M 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 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt/iron oxide-carbon nanotubes-ion exchange resin material M.
[embodiment 14]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.171 gram of Copper dichloride dihydrate, 0.119 (molar concentration is respectively 0.02 to rub to 50 ml deionized water solution of gram cobalt chloride hexahydrate and 0.270 gram of ferric chloride hexahydrate You/liter, 0.01 mol/L and 0.02 mol/L, molar concentration rate 2:1:2), water heating kettle is poured into stirring, and water heating kettle is through super It is placed in hydro-thermal furnace within sound oscillation 1 hour, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, pour into In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide is added Initiator stirs progress prepolymerization in 2 hours at 60 DEG C.150 milliliters of deionizations for being dissolved with 1.5 grams of polyvinyl alcohol are added Aqueous 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 98 DEG C are warming up to, is reacted 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into baking oven 80 DEG C of drying, sieving, tri compound microballoon N 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 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt/iron oxide-carbon nanotubes-ion exchange resin material N.
[embodiment 15]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.171 gram of Copper dichloride dihydrate, 0.238 (molar concentration is respectively 0.02 to rub to 50 ml deionized water solution of gram cobalt chloride hexahydrate and 0.135 gram of ferric chloride hexahydrate You/liter, 0.02 mol/L and 0.01 mol/L, molar concentration rate 2:2:1), water heating kettle is poured into stirring, and water heating kettle is through super It is placed in hydro-thermal furnace within sound oscillation 1 hour, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, pour into 250 In milliliter three-necked flask, 80.6 grams of p-chloromethyl styrenes are added, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide draw Agent is sent out, progress prepolymerization in 2 hours is stirred 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 O 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 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt/iron oxide-carbon nanotubes-ion exchange resin material O.
[embodiment 16]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.142 gram of Copper dichloride dihydrate, 0.226 (molar concentration is respectively 0.0167 to 50 ml deionized water solution of gram cobalt chloride hexahydrate and 0.199 gram of ferric chloride hexahydrate Mol/L, 0.0167 mol/L and 0.0167 mol/L, molar concentration rate 1:1:1), water heating kettle, hydro-thermal are poured into stirring 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, It pours into 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide is added Formyl initiator stirs progress prepolymerization in 2 hours at 60 DEG C.Be added be dissolved with 150 milliliters of 1.5 grams of polyvinyl alcohol go from Sub- aqueous 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, most After be warming 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 Interior 80 DEG C of drying, sieving, tri compound microballoon P 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 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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get trielement ion and sets Rouge 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt/iron oxide-carbon nanotubes-ion exchange resin material P.
[embodiment 17]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.107 gram of Copper dichloride dihydrate and 0.446 Gram cobalt chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0125 mol/L and 0.0375 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane The mixture (weight ratio between the two is 1:1) of base styrene and 4- (3- chloropropyl) styrene, 3.5 grams of divinylbenzenes With 0.1 gram of benzoyl peroxide initiator, progress prepolymerization in 2 hours is stirred at 60 DEG C.Addition has been dissolved with 1.5 grams of polyethylene 150 ml deionized water solution of alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It is warming up to 90 again DEG C, it reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, so After filter, be put into baking oven 80 DEG C of 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 cupric oxide/oxygen of strong basicity tri compound Change cobalt-carbon nanotubes-ion exchange resin material D2.
[embodiment 18]
It is poured into 2.5 grams of carboxylated dual openings multi-walled carbon nanotubes and has dissolved 0.107 gram of Copper dichloride dihydrate and 0.507 Gram ferric chloride hexahydrate 50 ml deionized water solution (molar concentration be respectively 0.0125 mol/L and 0.0375 mole/ Rise, 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, and 160 DEG C It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethane The mixture (weight ratio between the two is 1:1) of base styrene, 3.5 grams of divinylbenzenes and diallyl benzene, 0.1 gram of peroxide Change benzoyl initiator, progress prepolymerization in 2 hours is stirred at 60 DEG C.150 millis for being dissolved with 1.5 grams of polyvinyl alcohol are added Rise deionized water 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, reaction 5 is small When, 98 DEG C are finally warming up to, is reacted 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, puts Enter 80 DEG C of drying in baking oven, 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 cupric oxide/oxygen of strong basicity tri compound Change iron-carbon nanotubes-ion exchange resin material G2.
[embodiment 19]
It takes 0.595 gram of cobalt chloride hexahydrate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), soaks For stain into 2.5 grams of hydroxylating single pipe powders, water heating kettle is poured into stirring, and sonic oscillation 1 hour, 160 DEG C in hydro-thermal furnace It is lower to be kept for 24 hours, it is cooled to room temperature, is washed with deionized water, obtain nanometer cobalt oxide-carbon nanotubes binary composite sample.? In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide is added 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 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 nanometer cobalt oxide-nanometer of strong basicity tri compound Carbon pipe-ion exchange resin material B2.
[embodiment 20]
It takes 0.595 gram of cobalt chloride hexahydrate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), soaks For stain into 2.5 grams of carboxylated dual openings multi-wall carbon nano-tube pipe powders, water heating kettle is poured into stirring, and sonic oscillation 1 hour, in hydro-thermal furnace It is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, obtain nanometer cobalt oxide-compound sample of carbon nanotubes binary Product.In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of azo two is added Isobutyronitrile initiator stirs progress prepolymerization in 2 hours at 60 DEG C.It is added and has been dissolved with 150 milliliters of 1.5 grams of polyvinyl alcohol and goes Deionized water 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, 98 DEG C are finally warming up to, is reacted 6 hours.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into baking 80 DEG C of drying in case, sieving, 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 and receives to get the nanometer cobalt oxide-of strong basicity tri compound Rice carbon pipe-ion exchange resin material B3.
[embodiment 21]
Ion exchange resin material A~P, D2, G2, the B2 of strong basicity tri compound obtained by [Examples 1 to 2 0] are evaluated, The water content and basic group content of B3, 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 carboxyls are added Change dual openings multi-walled carbon nanotube and 0.1 gram of benzoyl peroxide initiator, progress prepolymerization in 2 hours is stirred at 60 DEG C.Add Enter to be 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, Reaction 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, it is poured out Supernatant 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 in 0.35-0.60mm model Enclose interior binary complex microsphere 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 carbon nanotubes-ion compound to get strong basicity binary is dried at 25 DEG C of room temperature Exchanger 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 carboxylated dual openings multi-wall carbon nano-tube pipe powders, water heating kettle is poured into stirring, and sonic oscillation 1 hour, in hydro-thermal furnace It is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, obtain nano tin dioxide-compound sample of carbon nanotubes binary Product.In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes are added, 3.5 grams of divinylbenzenes, 2.5 grams nano oxidized Tin-carbon nanotubes binary composite sample and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C. 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 80 DEG C, it 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, topple over Supernatant liquid out 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 in 0.35-0.60mm Binary complex microsphere R in range.
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 and receives to get the nano tin dioxide-of strong basicity tri compound Rice carbon pipe-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]
It takes 0.745 gram of zinc nitrate hexahydrate to be configured to 50 ml deionized water solution (0.05 mol/L of molar concentration), soaks For stain into 2.5 grams of carboxylated dual openings multi-wall carbon nano-tube pipe powders, water heating kettle is poured into stirring, and sonic oscillation 1 hour, in hydro-thermal furnace It is kept for 24 hours at 160 DEG C, is cooled to room temperature, is washed with deionized water, obtain nano zine oxide-compound sample of carbon nanotubes binary Product.In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes are added, 3.5 grams of divinylbenzenes, 2.5 grams nano oxidized Zinc-carbon nanotubes binary composite sample and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C. 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 80 DEG C, it 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, topple over Supernatant liquid out 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 in 0.35-0.60mm Binary complex microsphere S in range.
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 is added Score 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 When being equal to 1.0 to specific gravity, washing after adding sodium hydroxide transition, is further washed to neutral exchange to get binary compound ion and sets Rouge 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 and receives to get the nano zine oxide-of strong basicity tri compound Rice carbon pipe-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-carbon nanotubes-ion exchange resin material of strong basicity tri compound, it is characterized in that, with tree The parts by weight meter of rouge material gross weight, including following components:
(a) 70~90 parts of polymerized monomer；
(b) 5~15 parts of comonomer；
(c) 0.1~10 part of carbon nanotubes；
(d) 0.1~10 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 carbon nanotubes is selected from hydroxylating single-walled carbon nanotube, carboxylated dual openings multi-walled carbon nanotube or hydroxylating multi wall carbon At least one of nanotube；
The nano inorganic oxide group is selected from the nano-oxide of the first B metal or/and receiving for the 8th race's Ferrious material At least one of rice oxide；
The initiator in benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, isopropyl benzene hydroperoxide extremely Few one kind.
2. nano inorganic oxide-carbon nanotubes-ion exchange resin of strong basicity tri compound according to claim 1 Material, it is characterised in that first B metal is selected from copper.
3. nano inorganic oxide-carbon nanotubes-ion exchange resin of strong basicity tri compound according to claim 1 Material, it is characterised in that the metal of the 8th race's Ferrious material is selected from least one of iron, cobalt.
4. nano inorganic oxide-carbon nanotubes-ion of any one strong basicity tri compound according to claim 1~3 The preparation method of exchanger resin material, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into the water solution A that molar concentration is 0.01~3 mol/L；Its Described in nano inorganic oxide group be selected from the nano-oxide of the first B metal and/or receiving for the 8th race's Ferrious material At least one of corresponding soluble precursor salt of rice oxide；
(2) solution A is impregnated into carbon nanotubes, sonic oscillation 1~4 hour under room temperature, precipitating is added in high-pressure reactor Agent, 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 Oxide-carbon nanotubes binary material B；Wherein the precipitating reagent is selected from deionized water, ammonium hydroxide, urea, sodium hydroxide or carbonic acid At least one of hydrogen sodium.
(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-nanometer that will be prepared in the desired amount of polymerized monomer, comonomer, initiator and step (2) Carbon pipe 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-carbon nanotubes-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-carbon nanotubes-ion exchange resin of the strong basicity tri compound Material.
5. nano inorganic oxide-carbon nanotubes-ion exchange resin of the 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-carbon nanotubes-ion exchange resin of the 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-carbon nanotubes-ion exchange resin material of strong basicity tri compound according to claim 4 The preparation method of material, it is characterised in that the precipitating reagent is selected from least one of water or sodium hydroxide.
8. nano inorganic oxide-carbon nanotubes-ion exchange resin material of strong basicity tri compound according to claim 4 The preparation method of material, it is characterised in that the reagent and additive in polymerization is selected from least one of polyvinyl alcohol or gelatin；The sweller Selected from least one of methylene chloride or tetrahydrofuran；The amination reagent in front three amine salt or triethylamine salt at least It is a kind of.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110086960A1 (en) * 2009-10-14 2011-04-14 Cheng-Chien Yang Carbon nanotube compound and method for producing the same
CN103084581A (en) * 2013-01-08 2013-05-08 河南大学 Preparation method for copper nanowire
CN105006376A (en) * 2015-07-13 2015-10-28 华北电力大学 Preparation method of carbon nanotube and nickel oxide composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110086960A1 (en) * 2009-10-14 2011-04-14 Cheng-Chien Yang Carbon nanotube compound and method for producing the same
CN103084581A (en) * 2013-01-08 2013-05-08 河南大学 Preparation method for copper nanowire
CN105006376A (en) * 2015-07-13 2015-10-28 华北电力大学 Preparation method of carbon nanotube and nickel oxide composite material

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