CN109651553A - Strong basicity combination ion exchange resin material and preparation method thereof - Google Patents
Strong basicity combination ion exchange resin material and preparation method thereof Download PDFInfo
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- CN109651553A CN109651553A CN201710945977.4A CN201710945977A CN109651553A CN 109651553 A CN109651553 A CN 109651553A CN 201710945977 A CN201710945977 A CN 201710945977A CN 109651553 A CN109651553 A CN 109651553A
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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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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Abstract
The present invention relates to strong basicity combination ion exchange resin material 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) 72~87 parts of polymerized monomer；(b) 4~18 parts of comonomer；(c) 0.1~10 part of graphene；(d) 0.1~1 part of chain-transferring agent 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
Technical field
The present invention relates to strong basicity combination ion exchange resin materials and preparation method thereof.
Background technique
Strong-base anion-exchange resin can be used for water process, the purification of substance, concentration, separation, substance from molecular
Transformation, the decoloration of substance and catalyst etc..
The technology for developing strong-base anion-exchange resin both at home and abroad has some announcements.Document SU675056 is disclosed
The 2-mercaptobenzimidazole that 2% is introduced in chloromethyl polystyrene resin, then reacts again with trimethylamine and prepares strong alkali anion
Exchanger resin.Document JP01-75041 discloses the two amine type strong base anion exchangers of triethyl group with tricyclic structure.Document
JP07-24334 discloses the high temperature resistant anionite as adsorbent, it is characterized in that polystyrene resin phenyl ring
Methylene α-C between quaternary ammonium group is upper hydrogen-free.Document JP2002-212226 is disclosed to be contained between phenyl ring and quaternary nitrogen atoms
The polystyrene strong basic anion-exchange resin of long chain hydrocarbon groups benzyl oxide alkyl.
The preparation of industrial strong-base anion-exchange resin at present is the method synthetic copolymer for first using suspension polymerisation,
On the basis of further chloromethylation obtains chloromethyl resin, is made the transition and be made by aminating reaction.Such as document is " with attached
Add cross-linking method strong-base anion-exchange resin, Dandong chemical industry, the 1st phase in 1994 " it discloses with low cross linked polystyrene
For parent, through chloromethylation, methine crosslinking, strong alkalinity anion has been made in the trimethylamine amination of remaining chloromethyl
Exchanger resin.Although industrially synthesizing the reaction raw materials chloromethyl ether or dichloro of chloromethyl resin frequently with this method
Methyl ether has strong carcinogenesis；Chloromethylation the problems such as there are polysubstituted and crosslinkings simultaneously, so that chloromethyl resin
Structure is complicated changes, and the surface alkalinty activity group content of the anion exchange resin of acquisition is not often also high, greatly limits it
Catalytic activity.Disclose within 1993 it is a kind of using propagating radical by the free radical polymerization of the reversible passivation of living free radical polymerization
Reaction process, but it is emphasized that this polymerization technique can not avoid the biradical termination between Propagating Radical completely
It reacts, the reversible controllability of the propagation process in polymerization process is not high.(Michael K.Georges, Richard
P.N.Veregin, Peter M.Kazmaier, Gordon K.Hamer, Macromolecules, 1993,26,2987-2988)
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, it is compound to provide a kind of new strong basicity for and the correspondingly not high problem of activity in catalyst application process
Ion exchange resin material, the resin have basic functional group content high, 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
The preparation method of property combination ion exchange resin material.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: strong basicity compound ion exchange tree
Rouge material, it is characterized in that, in terms of the parts by weight of resin material gross weight, including following components:
(a) 72~87 parts of polymerized monomer；
(b) 4~18 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of chain-transferring agent 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, in iodo-methyl styrene or 2- iodobenzene ethylene at least
It is a kind of；
Polymerized monomer described in above-mentioned technical proposal more preferably from 2- iodobenzene ethylene and in iodo-methyl styrene at least
It is a kind of；The mixed polymerization monomer of the two has synergistic effect to the alkalinity for improving strong basicity combination ion exchange resin material；
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 least one of diallyl benzene and divinylbenzene；
The graphene is selected from least one of single-layer graphene or multi-layer graphene；
The chain-transferring agent group is selected from 1- phenyl iodoethane, iodoacetonitrile, 2- iodoethyl benzene, iodoform, 4- (2- iodo second
At least one of base) octyl benzene；
In above-mentioned technical proposal, the chain-transferring agent is more preferably from least one of 1- phenyl iodoethane and iodoform.
In above-mentioned technical proposal, the chain-transferring agent is more preferably from the mixture of 1- phenyl iodoethane and iodoform.The two
Mixing chain-transferring agent has synergistic effect to the alkalinity for improving strong basicity combination ion exchange 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 compound ion exchange tree
The preparation method of rouge material, comprising the following steps:
(1) reagent and additive in polymerization is made into the water solution A that weight percent concentration is 0.5~5%；The dosage of reagent and additive in polymerization is poly-
Close the 4~55% of monomer weight；
(2) the desired amount of polymerized monomer, comonomer, initiator and graphene are mixed into solution B；
(3) at room temperature, a part of prepared solution B is mixed with the desired amount of chain-transferring agent, and uses water at low temperature
Bath oscillation, is configured to solution C；
(4) remaining solution B is stirred with solution A, 35~55 DEG C prepolymerization 0.5~3 hour；Again to reactant
Solution C is added dropwise in system, after sealing is passed through argon gas displaced air, is warming up to 50~88 DEG C, reacts 3~8 hours, then heat to 80
~98 DEG C, react 4~10 hours curing moldings；After reaction, supernatant liquid is poured out, washed, filtering, is sieved at drying,
Composite graphite alkene-ion exchange resin beads of 0.35~0.60mm of collection cut size range；
(5) 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 3~16 hours at 25~38 DEG C；After reaction, it is washed, alkali is added and turns
Type, then it is washed to neutrality, obtain the strong basicity combination ion exchange resin material.
Wherein the reagent and additive in polymerization is in polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate
It is at least one；The sweller is selected from methylene chloride, 1,2- dichloroethanes, chloroform, N,N-dimethylformamide, dimethyl
At least one of sulfoxide or tetrahydrofuran；The amination reagent is selected from front three amine salt, triethylamine salt, diethylamine salt or tri-n-butylamine
At least one of 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 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, obtains strong basicity combination ion exchange resin material.
Using technical solution of the present invention, using chain-transferring agent and initiator, polymerized monomer styrene and comonomer hair
Life is free-radical polymerized, can adjust controllably to the extent of reaction of polymerization reaction, the polymerizing condition of reaction process is milder, and connects
Nearly industrial condition.Compared with traditional polymerization reaction experiment condition, have apparent advantage, realizes new strong basicity
The preparation of combination ion exchange resin material solves the basic activated base of strong basicity graphene combination ion exchange resin catalyst
Mass contg is low, and the correspondingly not high problem of activity in catalyst application process.Strong basicity compound ion in the present invention is handed over
Resin material is changed, has working condition mild, is easy to industrial amplification, basic functional group content is high, and activity is strong in reaction process
The characteristics of, preferable technical effect is achieved in actual application.
The basic group content assaying method of strong basicity combination ion exchange resin material of the invention is as follows: using hydrochloric acid
Standard solution titration takes 2.5 grams of resin material, 100 milliliters of hydrochloric acid standard solution of 0.1 mol/L is added, in 40 DEG C of temperature
It is cooling after 2 hours to spend lower heating water bath.25 milliliters of soak are taken, 50 ml deionized waters are added, 2~3 drop phenolphthalein instructions are added dropwise
Liquid.It is titrated with the standard solution of sodium hydroxide of 0.1 mol/L, records standard solution of sodium hydroxide volume V1Milliliter.Separately take resin
1 gram of 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]
Take 34 grams to iodo-methyl styrene, 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams
Single-layer graphene takes out 5 grams of mixed solutions after evenly mixing in stirring 1 hour, and 0.8 gram of iodoform, low temperature water-bath oscillation mixing is added
Solution A uniformly is obtained, remaining mixed solution is spare.500 milliliters of three-necked flask additions are taken to be dissolved with 2 grams of polyvinyl alcohol
Uniformly mixed stock solution is added dropwise in 200 ml deionized water solution, adjusts mixing speed, while being gradually warming up to 60 DEG C, in advance
After polymerization 1 hour, then the solution A prepared before being added dropwise into flask is warming up to 80 DEG C after sealing is passed through argon gas displaced air,
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
Layer 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 range
Interior complex microsphere A.
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, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature
A。
[embodiment 2]
Take 32 grams of 2- iodobenzene ethylene, 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams of single layer stones
Black alkene takes out 5 grams of mixed solutions after evenly mixing in stirring 1 hour, and 0.8 gram of iodoform is added, and low temperature water-bath oscillation is uniformly mixed
To solution A, remaining mixed solution is spare.It takes 500 milliliters of three-necked flasks to be added and has been dissolved with 200 milliliters of 2 grams of polyvinyl alcohol
Uniformly mixed stock solution is added dropwise in deionized water solution, adjusts mixing speed, while being gradually warming up to 60 DEG C, prepolymerization 1 is small
Shi Hou, then the solution A prepared before being added dropwise into flask after sealing is passed through argon gas displaced air, are warming up to 80 DEG C, reaction 5 is small
When；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,
It is washed with hot water, is then filtered, be put into 80 DEG C of drying in baking oven, be sieved, collection cut size is compound within the scope of 0.35-0.60mm
Microballoon B.
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, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature
B。
[embodiment 3]
Take 16 grams of 2- iodobenzene ethylene, 17 grams to iodo-methyl styrene, (to iodo-methyl styrene and 2- iodobenzene ethylene part
Number is than being 1:1), 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams of single-layer graphenes stir 1 hour
After evenly mixing, 5 grams of mixed solutions are taken out, 0.8 gram of iodoform is added, low temperature water-bath oscillation, which is uniformly mixed, obtains solution A, remaining
Mixed solution is spare.Take 500 milliliters of three-necked flasks that the 200 ml deionized water solution for being dissolved with 2 grams of polyvinyl alcohol, drop is added
Add uniformly mixed stock solution, mixing speed is adjusted, while being gradually warming up to 60 DEG C, after prepolymerization 1 hour, then into flask
The solution A prepared before being added dropwise after sealing is passed through argon gas displaced air, is warming up to 80 DEG C, reacts 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 C 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 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, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature
C。
[embodiment 4]
Take 16 grams of 2- iodobenzene ethylene, 17 grams to iodo-methyl styrene, (to iodo-methyl styrene and 2- iodobenzene ethylene part
Number is than being 1:1), 1.8 grams of diallyl benzene, 0.5 gram of benzoyl peroxide initiator and 2.5 grams of single-layer graphenes stir 1 hour
After evenly mixing, 5 grams of mixed solutions are taken out, 0.8 gram of iodoform is added, low temperature water-bath oscillation, which is uniformly mixed, obtains solution A, remaining
Mixed solution is spare.Take 500 milliliters of three-necked flasks that the 200 ml deionized water solution for being dissolved with 2 grams of polyvinyl alcohol, drop is added
Add uniformly mixed stock solution, mixing speed is adjusted, while being gradually warming up to 60 DEG C, after prepolymerization 1 hour, then into flask
The solution A prepared before being added dropwise after sealing is passed through argon gas displaced air, is warming up to 80 DEG C, reacts 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 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, the moisture graphene-ion exchange resin material compound to get strong basicity is dried at 25 DEG C of room temperature
D。
[embodiment 5]
Take 16 grams of 2- iodobenzene ethylene, 17 grams to iodo-methyl styrene, (to iodo-methyl styrene and 2- iodobenzene ethylene part
Number is than being 1:1), 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams of single-layer graphenes stir 1 hour
After evenly mixing, 5 grams of mixed solutions are taken out, 0.5 gram of 1- phenyl iodoethane is added, low temperature water-bath oscillation, which is uniformly mixed, obtains solution
A, remaining mixed solution are spare.Take 500 milliliters of three-necked flasks that 200 milliliters of deionizations for being dissolved with 2 grams of polyvinyl alcohol are added
Uniformly mixed stock solution is added dropwise in aqueous solution, adjusts mixing speed, while being gradually warming up to 60 DEG C, after prepolymerization 1 hour,
The solution A prepared before being added dropwise again into flask after sealing is passed through argon gas displaced air, is warming up to 80 DEG C, reacts 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
E。
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere E 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 E.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material E, 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
E。
[embodiment 6]
Take 16 grams of 2- iodobenzene ethylene, 17 grams to iodo-methyl styrene, (to iodo-methyl styrene and 2- iodobenzene ethylene part
Number is than being 1:1), 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams of single-layer graphenes stir 1 hour
After evenly mixing, 5 grams of mixed solutions are taken out, the mixed solution of 0.25 gram of 1- phenyl iodoethane and 0.4 gram of iodoform, water at low temperature is added
Bath oscillation, which is uniformly mixed, obtains solution A, and remaining mixed solution is spare.It takes 500 milliliters of three-necked flask additions to be dissolved with 2 grams to gather
Uniformly mixed stock solution is added dropwise in 200 ml deionized water solution of vinyl alcohol, adjusts mixing speed, while gradually heating up
To after 60 DEG C, prepolymerization 1 hour, then the solution A prepared before being added dropwise into flask, after sealing is passed through argon gas displaced air, rise
Temperature is reacted 5 hours to 80 DEG C；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to 98 DEG C, reacts 6 hours.Reaction terminates
Afterwards, 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-
Complex microsphere F within the scope of 0.60mm.
In 250 milliliters of three-necked flasks, 30 grams of complex microsphere F 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 F.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material F, 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
F。
[embodiment 7]
Evaluate the water content and alkali of ion exchange resin material A~E of strong basicity tri compound obtained by [Examples 1 to 6]
Property group content, the results are shown in Table 1.
[comparative example 1]
Take 34 grams to iodo-methyl styrene, 1.5 grams of divinylbenzenes, 0.5 gram of benzoyl peroxide initiator and 2.5 grams
Single-layer graphene it is spare to obtain solution A after evenly mixing in stirring 1 hour.500 milliliters of three-necked flask additions are taken to be dissolved with 2 grams
Uniformly mixed stock solution A is added dropwise in 200 ml deionized water solution of polyvinyl alcohol, adjusts mixing speed, while gradually rising
Temperature is reacted 5 hours to after 60 DEG C, prepolymerization 1 hour, being warming up to 80 DEG C；It is warming up to 90 DEG C again, reacts 5 hours, is finally warming up to
It 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 bakings in baking oven
It is dry, sieving, complex microsphere Q 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 Q 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 Q.
Last handling process is as follows: taking 50 milliliters of above-mentioned combination ion exchange resin material Q, 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
Q。
With [embodiment 7], the water content and basic group content of ion exchange resin material F are evaluated, the results are shown in Table 1.
Table 1
Claims (9)
1. strong basicity combination ion exchange resin material, it is characterized in that, in terms of the parts by weight of resin material gross weight, including it is following
Component:
(a) 72~87 parts of polymerized monomer；
(b) 4~18 parts of comonomer；
(c) 0.1~10 part of graphene；
(d) 0.1~1 part of chain-transferring agent 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 chain-transferring agent group is selected from 1- phenyl iodoethane, iodoacetonitrile, 2- iodoethyl benzene, iodoform, 4- (2- iodoethyl)
At least one of octyl benzene；
The initiator in benzoyl peroxide, azodiisobutyronitrile, lauroyl peroxide, isopropyl benzene hydroperoxide extremely
Few one kind.
2. strong basicity combination ion exchange resin material according to claim 1, it is characterized in that, the polymerized monomer choosing
From 4- (3- bromopropyl) styrene, 4- (4- chlorobutyl) styrene, 4- (4- brombutyl) styrene, to iodo-methyl styrene or
At least one of 2- iodobenzene ethylene.
3. strong basicity combination ion exchange resin material according to claim 2, it is characterized in that, the polymerized monomer choosing
From at least one of iodo-methyl styrene or 2- iodobenzene ethylene.
4. strong basicity combination ion exchange resin material according to claim 1, it is characterized in that, the chain-transferring agent group
It is selected from least one of 1- phenyl iodoethane or iodoform.
5. a kind of preparation method using any one strong basicity combination ion exchange resin material in Claims 1 to 4, including
Following steps:
(1) reagent and additive in polymerization is made into the water solution A that weight percent concentration is 0.5~5%；The dosage of reagent and additive in polymerization is that polymerization is single
The 4~55% of body weight；
(2) the desired amount of polymerized monomer, comonomer, initiator and graphene are mixed into solution B；
(3) at room temperature, a part of prepared solution B is mixed with the desired amount of chain-transferring agent, and is shaken using low temperature water-bath
It swings, is configured to solution C；
(4) remaining solution B is stirred with solution A, 35~55 DEG C prepolymerization 0.5~3 hour；Again into reaction system
Solution C is added dropwise, after sealing is passed through argon gas displaced air, is warming up to 50~88 DEG C, reacts 3~8 hours, then heat to 80~98
DEG C, react 4~10 hours curing moldings；After reaction, supernatant liquid is poured out, washed, filtering, dry, sieving are collected
Composite graphite alkene-ion exchange resin beads of 0.35~0.60mm of particle size range；
(5) 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 25~38 DEG C about 3~16 hours；After reaction, it is washed, alkali transition is added, then
It is washed to neutrality, obtains the strong basicity combination ion exchange resin material.
6. according to the preparation method of any one strong basicity combination ion exchange resin material in claim 5, it is characterised in that
The reagent and additive in polymerization is selected from least one of polyvinyl alcohol, gelatin, starch, methylcellulose, bentonite or calcium carbonate.
7. according to the preparation method of strong basicity combination ion exchange resin material in claim 5, it is characterised in that the swelling
Agent is in methylene chloride, 1,2- dichloroethanes, chloroform, N,N-dimethylformamide, dimethyl sulfoxide or tetrahydrofuran
At least one.
8. according to the preparation method of strong basicity combination ion exchange resin material in claim 5, it is characterised in that the amination
Reagent is selected from least one of front three amine salt, triethylamine salt, diethylamine salt or tri-n-butylamine salt；The alkali be selected from sodium hydroxide,
At least one of potassium hydroxide or sodium bicarbonate.
9. the preparation method of strong basicity combination ion exchange resin material according to claim 5, it is characterised in that described poly-
It closes auxiliary agent and is selected from least one of polyvinyl alcohol or gelatin；The sweller in methylene chloride or tetrahydrofuran at least
It is a kind of；The amination reagent is selected from least one of front three amine salt or triethylamine salt.
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| US20100021985A1 (en) * | 2007-03-20 | 2010-01-28 | The Regents Of The University Of California | Mechanical process for creating particles in fluid |
| CN102295727A (en) * | 2011-05-27 | 2011-12-28 | 北京化工大学 | Preparation method of polystyrene-g-acrylic acid ion exchange resin |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100021985A1 (en) * | 2007-03-20 | 2010-01-28 | The Regents Of The University Of California | Mechanical process for creating particles in fluid |
| CN102295727A (en) * | 2011-05-27 | 2011-12-28 | 北京化工大学 | Preparation method of polystyrene-g-acrylic acid ion exchange resin |
| 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 |
| 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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