CN109647515A - Strong basicity nano inorganic oxide-graphene-ion exchange resin material - Google Patents

Strong basicity nano inorganic oxide-graphene-ion exchange resin material Download PDF

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CN109647515A
CN109647515A CN201710945979.3A CN201710945979A CN109647515A CN 109647515 A CN109647515 A CN 109647515A CN 201710945979 A CN201710945979 A CN 201710945979A CN 109647515 A CN109647515 A CN 109647515A
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graphene
hours
ion exchange
exchange resin
resin material
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CN109647515B (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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • 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
    • C08K3/02—Elements
    • 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
    • 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
    • C08K2003/2251—Oxides; Hydroxides of metals of chromium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

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

Description

Strong basicity nano inorganic oxide-graphene-ion exchange resin material
Technical field
The present invention relates to strong basicity nano inorganic oxide-graphene-ion exchange resin materials and preparation method thereof.
Background technique
Graphene is a kind of novel nano-carbon material, in view of the high intensity of graphene, high conductivity, intensity it is big, can be soft The prominent property such as tough bending, graphene provide wide development space for novel, high performance polymer based composites. Composite material is prepared using graphene and polymer matrix bluk recombination, physical-mechanical properties, the electrical property of material can be obviously improved Matter etc., has broad application prospects.
Nano-oxide due to nano material peculiar property and have excellent performance, existing researcher is into one Step research and utilization nano-oxide such as is doped, coats, being modified at the composite material that can prepare different-shape, becomes new Research hotspot.Hydro-thermal method is the more one kind of research in the synthetic method of nano-oxide, as inorganic oxide solubility forerunner In the closed reaction vessel of body salt in a heated condition, using water as medium, many compounds show difference in reaction system In the physico-chemical property of room temperature, such as solubility increases, compound crystal structure easily makes the transition, the oxide products being recrystallized to give Grain is small and is evenly distributed, purity is high.Using polyethylene glycol as surfactant, oxalic acid cobalt precursor is prepared under hydrothermal conditions Obtain the Co of the higher different-shape of purity3O4, and even grain size (Yang Youping, Huang Kelong, Liu Rensheng etc., Central South University Journal, 2006,37,1103).Pires etc. is with SnCl2·2H2O is soluble precursor salt, is synthesized by microwave-assisted hydro-thermal method SnO powder can obtain the nanometer of different size and form by the method for adjusting hydrothermal synthesis time, temperature and its concentration Crystal (Pires F I, Joanni E, Savu R et al, Material Letters, 2008,62,239).Document CN106340633A, which discloses to report, obtains SnO using the synthetic method of hydro-thermal2/ carbon material and V2O5/ graphene composite wood Material, and SnO is further obtained by the method that ball milling is blended2/ carbon/V2O5/ graphene composite nano material.But above-mentioned technology In have the requirement of stronger hydrophily due to the material that hydro-thermal law system deposits nano-oxide, using liquid glucose or tool Have compared with strongly hydrophilic can graphene oxide, the evenly dispersed of aqueous solution and deposition materials can be promoted, thus obtain stablize it is equal Even suspension reaches preferable deposition effect, and its two different oxide is further passed through after being respectively synthesized preparation Physical mixed molding.Document CN104356258A, which is disclosed, reports the absorption property for using rare-earth element modified dealdehyding resin Method, still, in above-mentioned technology, after needing first to be synthetically prepared sulfonation acidic resins using polymerization technique, then by rare earth element nitre Acid solution is added in molded resin and is modified.Existing commercially available commercial 201 type strong-basicity styrene series anion exchange tree The full exchange capacity of rouge is about 3.4mmol/g.
Summary of the invention
Problem to be solved by this invention first is that the prior art there are strong basic ion exchange resin catalyst alkalinity is living Property group content it is low, and the correspondingly not high problem of activity in catalyst application process provides a kind of new strong basicity nanometer Inorganic oxide-graphene-ion exchange resin material, the resin have basic functional group content high, live in reaction process The strong feature of property.
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 Property nano inorganic oxide-graphene-ion exchange resin material preparation method.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: strong basicity nano inorganic oxide- Graphene-ion exchange resin material, it is characterized in that, in terms of the parts by weight of resin material gross weight, including following components:
(a) 70~85 parts of polymerized monomer；
(b) 3~15 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of nano inorganic oxide component；
(e) 0.1~10 part of initiator；
Wherein, the polymerized monomer is selected from at least one of the compound of flowering structure；
The polymerized monomer preferably is selected from p-chloromethyl styrene, 4- (3- chloropropyl) styrene, 4- (3- bromopropyl) benzene second Alkene, 4- (4- chlorobutyl) styrene, 4- (4- brombutyl) styrene, 4- (5- chlorine amyl) styrene or 4- (5- bromine amyl) benzene second At least one of alkene；
Polymerized monomer described in above-mentioned technical proposal is more preferably from p-chloromethyl styrene and 4- (3- chloropropyl) styrene；
The comonomer is selected from at least one of the compound of flowering structure；
The comonomer preferably is selected from ethyleneglycol dimethyacrylate, diallyl benzene, divinyl phenylmethane, two At least one of vinyl benzene；
Comonomer described in above-mentioned technical proposal is more preferably from diallyl benzene and divinylbenzene；The nano inorganic At least one in the nano-oxide of nano-oxide or/and the 8th race's noble metal of the oxide component selected from the 6th B metal Kind.
In above-mentioned technical proposal, preferred technical solution is that the 6th B metal is selected from chromium.
In above-mentioned technical proposal, preferred technical solution is that the 8th race's noble metal is selected from least one of palladium, platinum.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from the nano-oxide of the 6th B metal chromium The nano-oxide of chromium oxide and the 8th race's noble metal platinum；The molar ratio of chromium oxide and platinum oxide is (1:4)~(4:1), the two There is synergistic effect in terms of the high activity for improving resin material.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from the nano-oxide of the 6th B metal chromium The molar ratio of the nano-oxide of chromium oxide and the 8th race's precious metal palladium, chromium oxide and palladium oxide is (1:4)~(4:1)；The two There is synergistic effect in terms of the high activity for improving resin material.
In above-mentioned technical proposal, the nano inorganic oxide component preferably is selected from receiving for the 8th race's noble metal platinum and Metal Palladium The molar ratio of rice oxide, platinum oxide and palladium oxide is (1:4)~(4:1)；The two is in terms of the high activity for improving resin material With synergistic effect.
In above-mentioned technical proposal, the more preferable autoxidation chromium of the nano inorganic oxide component, platinum oxide and palladium oxide this The composition of three kinds of nano-oxides, the molar ratio of chromium oxide, platinum oxide and palladium oxide are 1:(0.25~4): (0.25~4), Three kinds of nano-oxides are used in conjunction with, and have 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: strong basicity nano inorganic oxide- Graphene-ion exchange resin material preparation method, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into the aqueous solution that molar concentration is 0.01~4 mol/L A；Wherein the nano inorganic oxide group is selected from the nano-oxide and/or the 8th race's noble metal of the 6th B metal At least one of corresponding soluble precursor salt of nano-oxide；
(2) solution A is impregnated into graphene, sonic oscillation 1~6 hour under room temperature, it is heavy to be added in high-pressure reactor Shallow lake agent, 100~500 DEG C at a temperature of hydrothermal decomposition 2~24 hours, then Slow cooling, be washed to room temperature, be made nanometer nothing Machine oxide-grapheme material B；Wherein the precipitating reagent is selected from deionized water, ammonium hydroxide, urea, sodium hydroxide or potassium hydroxide At least one of.
(3) reagent and additive in polymerization is made into the aqueous solution C that weight percent concentration is 0.3~3%；Wherein, the reagent and additive in polymerization 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) Grapheme 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 nano inorganic oxide-of 0.35~0.60mm of collection cut size range Graphene-ion exchange resin beads；
(6) amine of the sweller, 50~150% that are equivalent to complex microsphere weight 100~200% is added into complex microsphere 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 the strong basicity nano inorganic oxide-graphene-ion exchange 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 single-layer graphene and multi-layer graphene of use in the present invention can by epitaxial growth method, chemical vapour deposition technique, The methods of graphene oxide reduction method is prepared.This has been graphene preparation technology well known in the art, document CN201210561249.0 discloses report.
Ion exchange resin cross-linked scaffold involved in the present invention is polystyrene, synthesizes copolymerization skeleton by polymerization reaction Afterwards, functional group quaternary ammonium group is further introduced by aminating reaction.Specifically, inorganic oxide soluble precursor salt is direct It is generated by hydro-thermal method and nano-inorganic substance and loads to graphene surface, obtain that granularity is smaller and the nano inorganic oxidation that is uniformly dispersed Object-graphene complex.When the nano inorganic oxide-graphene complex participates in polymerization reaction, make nano inorganic oxide- Graphene complex and polymer carbon are grafted, and finally obtain nano inorganic oxide-graphene-ion exchange resin beads. Functional group quaternary ammonium group is introduced by aminating reaction, obtains strong basicity nano inorganic oxide-graphene-ion exchange resin material Material.
Using technical solution of the present invention, nanometer is dispersed by nano inorganic oxide load using the method for hydrothermal deposition Material graphene surface, and the graphene that deposited nano-oxide is applied in polymerization reaction, realize new strong basicity Nano inorganic oxide-graphene-ion exchange resin material preparation solves strong basicity graphene compound ion exchange tree The basic activated group content of rouge catalyst is low, and the correspondingly not high problem of activity in catalyst application process.In the present invention Strong basicity nano inorganic oxide-graphene-ion exchange resin material, have basic functional group content high, reacted The strong feature of activity, achieves preferable technical effect in actual application in journey.
Strong basicity nano inorganic oxide-graphene-ion exchange resin material basic group of the invention is containing measurement It is as follows to determine method: using hydrochloric acid standard solution titration, taking 2.5 grams of resin material, the normal hydrochloric acid that 0.1 mol/L is added is molten 100 milliliters of liquid, 40 DEG C at a temperature of heating water bath 2 hours after it is cooling.25 milliliters of soak are taken, 50 milliliters of deionizations are added 2~3 drop instructions phenolphthalein solutions are added dropwise in water.It is titrated with the standard solution of sodium hydroxide of 0.1 mol/L, record sodium hydroxide standard is molten Liquid accumulates V1Milliliter.Separately take 1 gram of resin material, 105 DEG C at a temperature of drying to constant weight, record quality m at this time1Gram.
The water content calculation formula of resin is
The basic group content calculation formula of resin surface is
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
The 50 ml deionized water solution for having dissolved 1.067 gram of two chloride hydrate palladium are poured into 2.5 grams of multi-layer graphenes Water heating kettle is poured into (0.1 mol/L of molar concentration), 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 being gradually warming up to It 80 DEG C, reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, incline Supernatant liquid is poured out, is washed with hot water, is then filtered, is put into 80 DEG C of drying in baking oven, sieving, collection cut size is in 0.35- Complex microsphere A within the scope of 0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere A and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin materials A.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin materials As, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide-graphene-amberlite Rouge materials A.
[embodiment 2]
It takes 2.001 grams of Chromium nitrate (Cr(NO3)3),nonahydrates to be configured to 50 ml deionized water solution (0.1 mol/L of molar concentration), soaks For stain into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 at 160 DEG C in hydro-thermal furnace Hour, it is cooled to room temperature, is washed with deionized water, obtain nano chromium oxide-graphene composite sample.In 250 milliliters of three mouthfuls of burnings In bottle, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, in 60 DEG C Lower stirring progress prepolymerization in 2 hours.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjust stirring Speed, while 80 DEG C are gradually warming up to, it reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reaction 6 Hour.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, is sieved, receive Collect complex microsphere B of the partial size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere B and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material B.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material B, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano chromium oxide-graphene-amberlite Rouge material B.
[embodiment 3]
Poured into 2.5 grams of multi-layer graphenes dissolved 2.590 gram of six hydration chloroplatinic acid deionized water solution it is (mole dense Spend 0.1 mol/L), water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, keeps at 160 DEG C It 24 hours, is cooled to room temperature, is washed with deionized water, pour into 250 milliliters of three-necked flasks, be added 80.6 grams to chloromethylbenzene second Alkene, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.It is added It has been dissolved with the 150 ml deionized water solution of 1.5 grams of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, instead It answers 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.After reaction, upper layer is poured out Liquid is washed with hot water, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, collection cut size is within the scope of 0.35-0.60mm Complex microsphere C.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere C and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material C.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material Cs, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get the nano oxidized platinum-graphene-amberlite of strong basicity Rouge material C.
[embodiment 4]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of two chloride hydrate palladium and 1.601 grams of Chromium nitrate (Cr(NO3)3),nonahydrates 50 ml deionized water solution (molar concentration is respectively 0.02 mol/L and 0.08 mol/L, molar concentration rate 1:4), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere D of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere D and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material D.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material D, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide/chromium oxide-graphene-ion Exchanger resin material D.
[embodiment 5]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.427 gram of two chloride hydrate palladium and 1.200 grams of Chromium nitrate (Cr(NO3)3),nonahydrates 50 ml deionized water solution (molar concentration is respectively 0.04 mol/L and 0.06 mol/L, molar concentration rate 2:3), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere E of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material E and strong basicity nano palladium oxide/chromium oxide-graphene-ion exchange resin material Expect the subsequent preparation process of E with embodiment 4.
[embodiment 6]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.533 gram of two chloride hydrate palladium and 1.000 grams of Chromium nitrate (Cr(NO3)3),nonahydrates 50 ml deionized water solution (molar concentration is respectively 0.05 mol/L and 0.05 mol/L, molar concentration rate 1:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere F of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material F and strong basicity nano palladium oxide/chromium oxide-graphene-ion exchange resin material Expect the subsequent preparation process of F with embodiment 4.
[embodiment 7]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.640 gram of two chloride hydrate palladium and 0.800 gram of Chromium nitrate (Cr(NO3)3),nonahydrate 50 ml deionized water solution (molar concentration is respectively 0.06 mol/L and 0.04 mol/L, molar concentration rate 3:2), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere G of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material G and strong basicity nano palladium oxide/chromium oxide-graphene-ion exchange resin material Expect the subsequent preparation process of G with embodiment 4.
[embodiment 8]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.853 gram of two chloride hydrate palladium and 0.400 gram of Chromium nitrate (Cr(NO3)3),nonahydrate 50 ml deionized water solution (molar concentration is respectively 0.08 mol/L and 0.02 mol/L, molar concentration rate 4:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere H of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material H and strong basicity nano palladium oxide/chromium oxide-graphene-ion exchange resin material Expect the subsequent preparation process of H with embodiment 4.
[embodiment 9]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of two chloride hydrate palladium and 2.072 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.02 mol/L and 0.08 mol/L, molar concentration rate 1:4), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere I of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere I and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material I.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material I, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide/platinum oxide-graphene-ion Exchanger resin material I.
[embodiment 10]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.427 gram of two chloride hydrate palladium and 1.554 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.04 mol/L and 0.06 mol/L, molar concentration rate 2:3), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere J of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material J and strong basicity nano palladium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of J with embodiment 9.
[embodiment 11]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.533 gram of two chloride hydrate palladium and 1.295 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.05 mol/L and 0.05 mol/L, molar concentration rate 1:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere K of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material K and strong basicity nano palladium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of K with embodiment 9.
[embodiment 12]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.640 gram of two chloride hydrate palladium and 1.036 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.06 mol/L and 0.04 mol/L, molar concentration rate 3:2), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere L of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material L and strong basicity nano palladium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of L with embodiment 9.
[embodiment 13]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.853 gram of two chloride hydrate palladium and 0.518 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.08 mol/L and 0.02 mol/L, molar concentration rate 4:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere M of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material M and strong basicity nano palladium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of M with embodiment 9.
[embodiment 14]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.400 gram of Chromium nitrate (Cr(NO3)3),nonahydrate and 2.072 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.02 mol/L and 0.08 mol/L, molar concentration rate 1:4), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere N of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere N and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material N.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material N, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano chromium oxide/platinum oxide-graphene-ion Exchanger resin material N.
[embodiment 15]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.800 gram of Chromium nitrate (Cr(NO3)3),nonahydrate and 1.554 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.04 mol/L and 0.06 mol/L, molar concentration rate 2:3), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere O of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material O and strong basicity nano chromium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of O with embodiment 14.
[embodiment 16]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 1.000 grams of Chromium nitrate (Cr(NO3)3),nonahydrates and 1.295 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.05 mol/L and 0.05 mol/L, molar concentration rate 1:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere P of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material P and strong basicity nano chromium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of P with embodiment 14.
[embodiment 17]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 1.200 grams of Chromium nitrate (Cr(NO3)3),nonahydrates and 1.036 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.06 mol/L and 0.04 mol/L, molar concentration rate 3:2), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere Q of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material Q and strong basicity nano chromium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of Q with embodiment 14.
[embodiment 18]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 1.601 grams of Chromium nitrate (Cr(NO3)3),nonahydrates and 0.518 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.08 mol/L and 0.02 mol/L, molar concentration rate 4:1), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinyls are added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere R of the collection cut size within the scope of 0.35-0.60mm.
Combination ion exchange resin material R and strong basicity nano chromium oxide/platinum oxide-graphene-ion exchange resin material Expect the subsequent preparation process of R with embodiment 14.
[embodiment 19]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of two chloride hydrate palladium, 0.800 gram of Chromium nitrate (Cr(NO3)3),nonahydrate With 1.036 gram six be hydrated chloroplatinic acid 50 ml deionized water solution (molar concentration be respectively 0.02 mol/L, 0.04 mole/ Liter and 0.04 mol/L, molar concentration rate 1:2:2), water heating kettle is poured into stirring, and water heating kettle was placed on through sonic oscillation 1 hour In hydro-thermal furnace, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, poured into 250 milliliters of three-necked flasks, add Enter 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator, stirs 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, together When be gradually warming 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.Instead After answering, 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 Complex microsphere S within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere S and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material S.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material S, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide/chromium oxide/platinum oxide-graphite Alkene-ion exchange resin material S.
[embodiment 20]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.427 gram of two chloride hydrate palladium, 0.400 gram of Chromium nitrate (Cr(NO3)3),nonahydrate With 1.036 gram six be hydrated chloroplatinic acid 50 ml deionized water solution (molar concentration be respectively 0.04 mol/L, 0.02 mole/ Liter and 0.04 mol/L, molar concentration rate 2:1:2), water heating kettle is poured into stirring, and water heating kettle was placed on through sonic oscillation 1 hour In hydro-thermal furnace, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, poured into 250 milliliters of three-necked flasks, add Enter 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator, stirs 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, together When be gradually warming 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.Instead After answering, 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 Complex microsphere T within the scope of 0.35-0.60mm.
Combination ion exchange resin material T and strong basicity nano palladium oxide/chromium oxide/platinum oxide-graphene-ion exchange The subsequent preparation process of resin material T is the same as embodiment 19.
[embodiment 21]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.427 gram of two chloride hydrate palladium, 0.800 gram of Chromium nitrate (Cr(NO3)3),nonahydrate With 0.518 gram six be hydrated chloroplatinic acid 50 ml deionized water solution (molar concentration be respectively 0.04 mol/L, 0.04 mole/ Liter and 0.02 mol/L, molar concentration rate 2:2:1), water heating kettle is poured into stirring, and water heating kettle was placed on through sonic oscillation 1 hour In hydro-thermal furnace, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, poured into 250 milliliters of three-necked flasks, add Enter 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator, stirs 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, together When be gradually warming 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.Instead After answering, 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 Complex microsphere U within the scope of 0.35-0.60mm.
Combination ion exchange resin material U and strong basicity nano palladium oxide/chromium oxide/platinum oxide-graphene-ion exchange The subsequent preparation process of resin material U is the same as embodiment 19.
[embodiment 22]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.352 gram of two chloride hydrate palladium, 0.660 gram of Chromium nitrate (Cr(NO3)3),nonahydrate (molar concentration is respectively 0.033 mol/L, 0.033 rubs the 50 ml deionized water solution for being hydrated chloroplatinic acid with 0.855 gram six You/liter and 0.033 mol/L, molar concentration rate 1:1:1), stir pour into water heating kettle, water heating kettle is after sonic oscillation 1 hour It is placed in hydro-thermal furnace, is kept for 24 hours at 160 DEG C, be cooled to room temperature, be washed with deionized water, pour into 250 milliliters of three-necked flasks It is interior, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of benzoyl peroxide initiator is added, at 60 DEG C Stir 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 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 Complex microsphere V of the partial size within the scope of 0.35-0.60mm.
Combination ion exchange resin material V and strong basicity nano palladium oxide/chromium oxide/platinum oxide-graphene-ion exchange The subsequent preparation process of resin material V is the same as embodiment 19.
[embodiment 23]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of two chloride hydrate palladium and 1.601 grams of Chromium nitrate (Cr(NO3)3),nonahydrates 50 ml deionized water solution (molar concentration is respectively 0.02 mol/L and 0.08 mol/L, molar concentration rate 1:4), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, is added 85.7 grams of 4- (3- chloropropyl) styrene, and 3.5 gram two Vinyl benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 150 ml deionized water solution of gram polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；Again 90 DEG C are warming up to, is reacted 5 hours, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, with heat Then water washing filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere of the collection cut size within the scope of 0.35-0.60mm D2。
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere D2 and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material D2.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material D2, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide/chromium oxide-graphene-ion Exchanger resin material D2.
[embodiment 24]
It is poured into 2.5 grams of multi-layer graphenes and has dissolved 0.213 gram of two chloride hydrate palladium and 2.072 gram of six hydration chloroplatinic acid 50 ml deionized water solution (molar concentration is respectively 0.02 mol/L and 0.08 mol/L, molar concentration rate 1:4), Water heating kettle is poured into stirring, and water heating kettle was placed in hydro-thermal furnace through sonic oscillation 1 hour, is kept for 24 hours at 160 DEG C, is cooled to room Temperature is washed with deionized water, and is poured into 250 milliliters of three-necked flasks, and 80.6 grams of p-chloromethyl styrenes, 3.8 gram of two propylene is added Base benzene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams and has gathered 150 ml deionized water solution of vinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It heats up again It to 90 DEG C, reacts 5 hours, is finally warming up to 98 DEG C, react 6 hours.After reaction, supernatant liquid is poured out, uses hot water wash It washs, then filters, be put into 80 DEG C of drying in baking oven, sieving, complex microsphere I2 of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere I2 and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material I2.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material I2, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano palladium oxide/platinum oxide-graphene-ion Exchanger resin material I2.
[embodiment 25]
It takes 2.001 grams of Chromium nitrate (Cr(NO3)3),nonahydrates to be configured to 50 ml deionized water solution (0.1 mol/L of molar concentration), soaks For stain into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 at 160 DEG C in hydro-thermal furnace Hour, it is cooled to room temperature, is washed with deionized water, obtain nano chromium oxide-graphene composite sample.In 250 milliliters of three mouthfuls of burnings In bottle, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes and 0.1 gram of azodiisobutyronitrile initiator is added, in 60 DEG C Lower stirring progress prepolymerization in 2 hours.The 150 ml deionized water solution for being dissolved with 1.5 grams of polyvinyl alcohol are added.Adjust stirring Speed, while 80 DEG C are gradually warming up to, it reacts 5 hours；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reaction 6 Hour.After reaction, supernatant liquid is poured out, is washed with hot water, then filters, is put into 80 DEG C of drying in baking oven, is sieved, receive Collect complex microsphere B2 of the partial size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere B2 and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material B2.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material B2, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano chromium oxide-graphene-amberlite Rouge material B2.
[embodiment 26]
Evaluate strong basic ion exchange resin materials A~V, D2, I2, the water content and alkali of B2 obtained by [Examples 1 to 2 5] Property group content, the results are shown in Table 1.
[comparative example 1]
In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of multilayers are added Graphene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams 150 ml deionized water solution of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It rises again Temperature is reacted 5 hours to 90 DEG C, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, uses hot water Washing, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, complex microsphere W of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere W and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material W.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material W, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature W。
With [embodiment 26], the water content and basic group content of ion exchange resin material W are evaluated, the results are shown in Table 1.
[comparative example 2]
In 250 milliliters of three-necked flasks, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of multilayers are added Graphene and 0.1 gram of benzoyl peroxide initiator stir progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams 150 ml deionized water solution of polyvinyl alcohol.Mixing speed is adjusted, while being gradually warming up to 80 DEG C, is reacted 5 hours；It rises again Temperature is reacted 5 hours to 90 DEG C, is finally warming up to 98 DEG C, is reacted 6 hours.After reaction, supernatant liquid is poured out, uses hot water Washing, is then filtered, and is put into 80 DEG C of drying in baking oven, sieving, complex microsphere of the collection cut size within the scope of 0.35-0.60mm W2。
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere W2 and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material W2.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material W2, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature W2。
With [embodiment 26], the water content and basic group content of ion exchange resin material W2 are evaluated, the results are shown in Table 1.
[comparative example 3]
It takes 1.754 grams of stannic chloride pentahydrates to be configured to 50 ml deionized water solution (0.1 mol/L of molar concentration), soaks For stain into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, keeps 24 at 160 DEG C in hydro-thermal furnace Hour, it is cooled to room temperature, is washed with deionized water, obtain nano tin dioxide-graphene composite sample.250 milliliters of three-necked flasks It is interior, be added 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of nano tin dioxides-graphene composite sample and 0.1 gram of benzoyl peroxide initiator stirs progress prepolymerization in 2 hours at 60 DEG C.Addition has been dissolved with 1.5 grams of polyvinyl alcohol 150 ml 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 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 Filtering is put into 80 DEG C of drying in baking oven, sieving, complex microsphere X of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere X and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material X.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material X, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano tin dioxide-graphene-amberlite Rouge material X.
With [embodiment 26], the water content and basic group content of ion exchange resin material X are evaluated, the results are shown in Table 1.
[comparative example 4]
1.352 grams of Iron(III) chloride hexahydrates are taken to be configured to 50 ml deionized water solution (0.1 mol/L of molar concentration), It is impregnated into 2.5 grams of multi-layer graphene powder, water heating kettle is poured into stirring, sonic oscillation 1 hour, is kept in hydro-thermal furnace at 160 DEG C It 24 hours, is cooled to room temperature, is washed with deionized water, obtain nano iron oxide-graphene composite sample.250 milliliters of three mouthfuls of burnings In bottle, 80.6 grams of p-chloromethyl styrenes, 3.5 grams of divinylbenzenes, 2.5 grams of nano iron oxides-graphene composite sample are added 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, complex microsphere Y of the collection cut size within the scope of 0.35-0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere Y and 50 milliliters of dichloroethanes are added, bath temperature is adjusted It is 30 DEG C, complex microsphere is allowed to be swollen at such a temperature 2 hours.Then 27 grams of trimethylamine hydrochlorides are added and mass fraction is 20% 130 milliliters of sodium hydroxide solution, 30 DEG C or so react about 8 hours.After reaction, specific gravity is gradually diluted with water to be equal to When 1.0, washing after adding sodium hydroxide transition, is washed to neutrality further to get combination ion exchange resin material Y.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material Y, is impregnated with 200 milliliters of methanol It is washed afterwards with 700 ml deionized waters.It is then charged into the glass column with husky core, resin, deionized water is washed with deionized Flow velocity is 5 ml/mins, and the processing time is 30 minutes；Resin is washed with the HCl solution of 0.75 mol/L, flow velocity is 2 milliliters/ Minute, the processing time is 90 minutes；Then resin is washed with deionized until eluate is neutrality；With 0.3 mol/L NaOH solution washs resin, and flow velocity is 1.7 ml/mins, and the processing time is 200 minutes；Then resin is washed with deionized Until eluate is neutrality, moisture is dried at 25 DEG C of room temperature to get strong basicity nano iron oxide-graphene-amberlite Rouge material Y.
With [embodiment 26], the water content and basic group content of ion exchange resin material Y are evaluated, the results are shown in Table 1.
Table 1

Claims (8)

1. strong basicity nano inorganic oxide-graphene-ion exchange resin material, it is characterized in that, with resin material gross weight Parts by weight meter, including following components:
(a) 70~85 parts of polymerized monomer；
(b) 3~15 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of nano inorganic oxide component；
(e) 0.1~10 part of initiator；
Wherein, the polymerized monomer is selected from at least one of the compound of flowering structure；
The comonomer is selected from at least one of the compound of flowering structure；
The graphene is selected from least one of single-layer graphene or multi-layer graphene；
The nano inorganic oxide group is selected from the nano-oxide of the 6th B metal or/and the nanometer of the 8th race's noble metal At least one of oxide；
The initiator in benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, isopropyl benzene hydroperoxide extremely Few one kind.
2. strong basicity nano inorganic oxide-graphene-ion exchange resin material according to claim 1, feature It is that the 6th B metal is selected from chromium.
3. strong basicity nano inorganic oxide-graphene-ion exchange resin material according to claim 1, feature It is that the 8th race's noble metal is selected from least one of palladium, platinum.
4. a kind of using strong basicity nano inorganic oxide-graphene-ion exchange resin material any in claims 1 to 3 Preparation method, comprising the following steps:
(1) nano inorganic oxide soluble precursor salt is made into the water solution A that molar concentration is 0.01~4 mol/L；Its Described in nano inorganic oxide group be selected from the nano-oxide of the 6th B metal and/or the nanometer of the 8th race's noble metal At least one of corresponding soluble precursor salt of oxide；
(2) solution A being impregnated into graphene, sonic oscillation 1~6 hour, is added precipitating reagent in high-pressure reactor under room temperature, 100~500 DEG C at a temperature of sealing thermal insulation 2~24 hours, then Slow cooling, be washed to room temperature, be made nano inorganic oxygen Compound-grapheme material B；Wherein the precipitating reagent is in deionized water, ammonium hydroxide, urea, sodium hydroxide or potassium hydroxide It is at least one.
(3) reagent and additive in polymerization is made into the aqueous solution C that weight percent concentration is 0.3~3%；Wherein, the reagent and additive in polymerization is selected from At least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate；The dosage of reagent and additive in polymerization is polymerization The 5~50% of monomer weight；
(4) nano inorganic oxide-graphite that will be prepared in the desired amount of polymerized monomer, comonomer, initiator and step (2) Alkene 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, nano inorganic oxide-graphite of 0.35~0.60mm of collection cut size range Alkene-ion exchange resin beads；
(6) the amination examination of the sweller, 50~150% that are equivalent to complex microsphere weight 100~200% is added into complex microsphere Agent and 50~150% alkali, reacted at 25~40 DEG C about 3~20 hours；After reaction, it is washed, alkali transition is added, then It is washed to neutrality, obtains the strong basicity nano inorganic oxide-graphene-ion exchange resin material.
5. according to any one strong basicity nano inorganic oxide-graphene-ion exchange resin material system in claim 4 Preparation Method, it is characterised in that the sweller is selected from methylene chloride, 1,2- dichloroethanes, chloroform, N, N- dimethyl formyl At least one of amine, dimethyl sulfoxide or tetrahydrofuran.
6. according to any one strong basicity nano inorganic oxide-graphene-ion exchange resin material system in claim 4 Preparation Method, it is characterised in that the amination reagent in front three amine salt, triethylamine salt, diethylamine salt or tri-n-butylamine salt at least It is a kind of；The alkali is selected from least one of sodium hydroxide, potassium hydroxide or sodium bicarbonate.
7. strong basicity nano inorganic oxide-graphene-ion exchange resin material preparation side according to claim 4 Method, it is characterised in that the precipitating reagent is selected from least one of water or sodium hydroxide.
8. strong basicity nano inorganic oxide-graphene-ion exchange resin material preparation side according to claim 4 Method, it is characterised in that the reagent and additive in polymerization is selected from least one of polyvinyl alcohol or gelatin；The sweller is selected from dichloromethane At least one of alkane or tetrahydrofuran；The amination reagent is selected from least one of front three amine salt or triethylamine salt.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140065515A (en) * 2012-11-15 2014-05-30 한국에너지기술연구원 Cathode catalyst for lithium-air battery, method of manufacturing the same, and lithium-air battery comprising the same
CN104558359A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of strong basic graphene composite resin material
CN104558360A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Strong-alkalinity composite ion exchange resin material and preparation method thereof
CN104926975A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Strong alkaline composite resin material and preparation method thereof
CN105367700A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Strong-basicity ternary composite metal-graphene-ion exchange resin material and preparing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140065515A (en) * 2012-11-15 2014-05-30 한국에너지기술연구원 Cathode catalyst for lithium-air battery, method of manufacturing the same, and lithium-air battery comprising the same
CN104558359A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Preparation method of strong basic graphene composite resin material
CN104558360A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Strong-alkalinity composite ion exchange resin material and preparation method thereof
CN104926975A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Strong alkaline composite resin material and preparation method thereof
CN105367700A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Strong-basicity ternary composite metal-graphene-ion exchange resin material and preparing method thereof

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