CN113698554A - With nano SiO2Anion exchange resin as inner core and preparation method thereof - Google Patents
With nano SiO2Anion exchange resin as inner core and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 76
- 229920005989 resin Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 75
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 75
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 75
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 75
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 52
- 150000003440 styrenes Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 18
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 239000000805 composite resin Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 150000002357 guanidines Chemical class 0.000 claims abstract description 11
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 4
- 239000011147 inorganic material Substances 0.000 claims abstract description 4
- 229920000620 organic polymer Polymers 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229920000159 gelatin Polymers 0.000 claims description 8
- 239000008273 gelatin Substances 0.000 claims description 8
- 235000019322 gelatine Nutrition 0.000 claims description 8
- 235000011852 gelatine desserts Nutrition 0.000 claims description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 8
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 239000005662 Paraffin oil Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 4
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract description 9
- 238000007265 chloromethylation reaction Methods 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000005498 polishing Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- 238000005303 weighing Methods 0.000 description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229960004198 guanidine Drugs 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- -1 quaternary ammonium ions Chemical class 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910006362 δ-Bi2O3 Inorganic materials 0.000 description 1
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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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- 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
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
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- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a method for preparing nano SiO2Anion exchange resin as kernel and its preparation method, the anion exchange resin is organic polymer and inorganic material compound with core-shell structure, and its kernel is nano SiO2And the shell is chloromethylated styrene resin. The preparation method of the anion exchange resin utilizes KH570 to nano SiO2Performing surface hydrophobic modification to obtain KH570 coupled nano SiO2Then, againSuspension polymerization with p-chloromethyl styrene to obtain nano SiO2Polystyrene chloromethylation composite resin, and reacting with guanidine salt to obtain anion exchange resin. The anion exchange resin has higher structural strength, larger alkali exchange capacity and better high temperature resistance, and has potential application prospects in the aspects of ion exchange, organic catalytic reaction, condensate polishing of air cooling units of thermal power plants, medicament intermediate decoloration, removal of impurity ions in industrial wastewater and the like in a high-temperature environment.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a nano SiO2Anion exchange resin as inner core and its preparation process.
Background
The polystyrene anion exchange resin is widely used in the fields of organic catalytic reaction, condensate polishing of air cooling units of thermal power plants, drug intermediate decoloring, impurity ion removal of industrial wastewater and the like. But commercially available OH-The structure of the strong basic anion exchange resin contains hydroxyl benzyl trialkyl ammonium, namely quaternary ammonium groups, when the use temperature exceeds 60 ℃, the quaternary ammonium groups of the quaternary ammonium strong basic resin can generate Hoffman degradation reaction to cause the quaternary ammonium groups to fall off or to be converted into weak base groups from strong base groups, so that the strong basic anion exchange resin is inactivated, the structural strength of the resin is reduced, the exchange capacity is reduced, and the use range is limited.
The research work for improving the heat resistance of polystyrene strong base anion exchange resin has been concerned by researchers in various countries. The method adopts measures to enhance the bond energy of quaternary ammonium ions and improve the decomposition activation energy of the quaternary ammonium ions, is an effective way for achieving the purpose of improving the thermal stability of the polystyrene strong base anion exchange resin, and mainly comprises the following 3 ways: (1) by modification of the hydrocarbon radical R bound to the nitrogen atom of a quaternary ammonium1、R2、R3A group; (2) the electronic effect of the benzene ring is changed (an electron-withdrawing substituent or an electron-donating substituent is introduced), so that the activation energy of C-N bond breakage between a methylene and a nitrogen atom connected with the benzene ring is increased, and the benzene ring is more stable; (3) a phenylene group between the benzene ring and the quaternary ammonium salt groupThe methyl group is changed into long-chain alkyl group, thus obtaining the novel polystyrene strong base anion exchange resin. Mitsubishi chemical corporation developed a strong base anion exchange resin with a long carbon chain spacer structure that improved the thermal stability of the resin by introducing the long carbon chain spacer into the benzene ring and quaternary nitrogen atoms of the resin. The strong base anion exchange resin with a long spacer arm is also synthesized by people such as Chenqun, Wang \29856, Liu Ying Chun and the like in China through different synthesis paths, and the thermal stability of the resin is greatly improved. From the current research situation, the structure modification research of the strong base anion exchange resin mainly changes the connection mode of quaternary ammonium groups and resin skeletons, and is limited by the quaternary ammonium group structure, the thermal stability of the resin is not improved fundamentally, and most importantly, the synthesis process of the resin is complex, and the large-scale industrial production and application of the resin are limited.
The guanidine compound is an organic base with the alkalinity equivalent to NaOH, three nitrogen atoms in the cation of the guanidine compound are symmetrically distributed around carbon atoms, and the thermal stability of the guanidine compound is very high due to the existing conjugation effect. The application of the anion exchange resin on the ion exchange resin can obviously improve the temperature resistance of the anion exchange resin. Patent CN201110109696.8 discloses a high-temperature resistant guanidyl strong base anion exchange resin and a synthesis method thereof. The resin is prepared mainly by utilizing the chemical reaction between chloromethyl on a chloromethylated polystyrene type resin framework and free guanidine. However, the preparation process of the guanidino resin uses extremely unstable free guanidine, so that the preparation difficulty is increased, and the conversion rate of chemical bonding reaction between guanidino and chloromethyl in the synthesis process is low. Patent CN109180851.6 discloses another preparation method of high temperature resistant guanidyl strong base resin, which utilizes KH570 to synthesize face cubic phase delta-Bi by microwave method2O3Surface hydrophobic modification is carried out, and delta-Bi is prepared by suspension polymerization2O3The resin white ball core-shell compound is subjected to chloromethylation reaction and then reacts with guanidine hydrochloride to prepare the high-temperature resistant guanidyl strong base resin. But using the microwave method to synthesize the face cubic phase delta-Bi2O3The raw materials are not easy to obtain, the synthesis essentially adopts a microwave method to replace a hydrothermal method,the microwave has limited penetration depth into the medium, is harmful to human body and is not suitable for large-scale application, and in addition, the quantity and the sites of introduced chloromethyl groups cannot be directionally controlled in the white ball chloromethylation process, so that the final strong base exchange amount is influenced.
Therefore, the invention is prepared by the method for preparing the nano material SiO which is industrially produced on a large scale and is most widely applied at present2Hydrophobic modification and direct quantitative polymerization of p-chloromethyl styrene monomer to obtain chloromethylated styrene resin compound, and reaction with guanidine salt to obtain nano SiO2The anion exchange resin with the inner core ensures that the synthesis process of the resin is simpler, the structural strength, the strong base exchange capacity and the thermal stability of the resin are improved, and compared with the commercialized quaternary ammonium type anion exchange resin, the production process and the production cost are not obviously changed, thereby having important significance for industrial production and application.
Disclosure of Invention
The invention provides a method for preparing nano SiO2The anion exchange resin as the inner core has good temperature resistance, and compared with the existing method, the synthesis process of the resin is simple, and the obtained resin has high conversion rate, controllable strong base exchange amount, strong heat-resistant stability and high structural strength.
In order to solve the technical problems, the invention adopts the following technical scheme:
with nano SiO2Anion exchange resin as kernel, which is a compound of organic polymer and inorganic material with core-shell structure, and the kernel is nano SiO2And the shell is chloromethylated styrene resin.
The SiO is nano-sized2The preparation method of the anion exchange resin with the inner core comprises the following steps:
step a) preparing nano SiO2Drying to obtain dry nano SiO2；
Step b) drying the nano SiO obtained in step a)2Adding the mixture into a hydrophobic modifier solution, ultrasonically dispersing for 2-4 h, adjusting the pH value of the system to 3.4-4.0 by using oxalic acid, and stirring for reactionCentrifuging for 4-8 h, washing with absolute ethyl alcohol, and vacuum drying at 60-80 ℃ for 6-8 h to obtain the hydrophobically modified nano SiO2；
Step c), mixing the components in a mass ratio of 0.2-1: 120-180: 220-450: 25-60 of initiator, pore-forming agent, p-chloromethyl styrene and the hydrophobic modified nano SiO obtained in step b)2Stirring uniformly to obtain an oil phase reaction solution; and then, mixing the raw materials in a mass ratio of 1-2: 20-25: uniformly mixing 100-150 parts of gelatin, sodium chloride and deionized water to obtain a water-phase reaction solution, and cooling to 40-50 ℃; mixing the components in a mass ratio of 1: 2-1: 2.5 mixing the oil-phase reaction liquid with the water-phase reaction liquid; heating to 50-60 ℃, dropwise adding a 1.0 wt% methylene blue ethanol solution with the mass fraction of 0.001-0.003: 1 to the oil phase reaction liquid, and adding a p-chloromethyl styrene solution with the mass ratio of 0.02: 1-0.1: 1, slowly heating to 90-95 ℃, stirring for reaction for 12-24 hours, extracting by using ethanol, drying and screening to obtain nano SiO2Chloromethylated styrene resin complex;
step d) mixing the nano SiO in step c)2Adding a chloromethylated styrene resin composite into a solvent for swelling for 2-4 h, adding guanidinium dissolved in the solvent in advance, adding a sodium ethoxide ethanol solution, heating to 80-100 ℃, reacting for 4-8 h, filtering, washing with a large amount of deionized water, and vacuum drying at 60-80 ℃ for 8-12 h to obtain the nano SiO2An anion exchange resin with an inner core.
The nano SiO in the step a)2The particle size range of 30-100 nm, and the drying method comprises the following steps: mixing nano SiO2Drying in a constant temperature blast drying oven, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2。
The hydrophobic modifier solution in the step b) is a KH570 ethanol solution with the mass fraction of 15-25 wt%, and the hydrophobic modifier solution and the nano SiO2The mass ratio of (A) to (B) is 20: 1-40: 1, the dosage of ethanol used in washing is 30-50 times of the mass of the hydrophobic modifier solution.
The initiator in the step c) is one of azobisisobutyronitrile, benzoyl peroxide, ammonium persulfate and potassium persulfate, and the pore-forming agent is one of paraffin oil, gasoline and toluene.
The swelling agent in the step d) is one of N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) and Tetrahydrofuran (THF).
The guanidine salt in the step d) is one of guanidine hydrochloride, guanidine carbonate, guanidine acetate and guanidine nitrate.
Guanidine salt and nano SiO in step d)2The mass ratio of the chloromethylated styrene resin composite is 1.5: 1-5: 1, and the mass of the solvent is equal to that of the nano SiO2The mass ratio of the chloromethylated styrene resin compound is 5-10: 1, the concentration of the sodium ethoxide ethanol solution is 20-30 wt%, and the mass ratio of the sodium ethoxide ethanol solution to the guanidine salt is 2: 1-5: 1.
the invention has the beneficial effects that:
compared with the prior art, the invention introduces the nano material SiO which is produced industrially in large scale and has the most extensive application in the polystyrene type ion exchange resin2First, nano SiO2The introduction of the nano-SiO resin realizes the molecular-level composition of organic high molecular materials and inorganic materials, enhances the structural strength of the resin, and introduces nano-SiO with different nano-sizes2Regulating and controlling the particle size of the resin, and preparing nano SiO2The excellent heat resistance of the ion exchange resin can improve the heat stability of the ion exchange resin. In addition, p-chloromethyl styrene monomer and nano SiO subjected to hydrophobic modification are directly used2Quantitatively polymerizing to obtain chloromethylated resin compound with a core-shell structure, and reacting with guanidine salt to obtain nano SiO2The resin is anion exchange resin with an inner core, the synthesis process of the resin is simpler, the obtained resin has high conversion rate, controllable strong base exchange amount, strong heat-resistant stability and high structural strength, and compared with the commercialized quaternary ammonium type anion exchange resin, the production process and the production cost are not obviously changed, thereby having important significance for industrial production and application. The anion exchange resin has potential application prospects in the fields of organic catalytic reaction, fine treatment of condensed water of an air cooling unit of a thermal power plant, decoloration of drug intermediates, removal of impurity ions in industrial wastewater and the like.
Drawings
FIG. 1 shows an embodiment of the present invention with nano SiO2A process flow diagram for preparing anion exchange resin with an inner core;
FIG. 2 shows a nanometer SiO solid prepared in example 1 of the present invention2Anion exchange resin morphology map for inner core
FIG. 3 shows the nano SiO prepared in example 2 of the present invention2Anion exchange resin morphology map for inner core
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Example 1
Weighing 100g of nano SiO with the particle size of 30nm2Drying in an electrothermal constant-temperature blast drying oven, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2And (5) standby.
Weighing 20g of dried nano SiO2Adding into 500g KH570 ethanol solution with mass fraction of 20 wt%, ultrasonically dispersing for 2h, adjusting pH to 3.5 with oxalic acid, stirring for 5h, centrifuging, washing with 800g anhydrous ethanol, and vacuum drying at 60 deg.C for 6h to obtain hydrophobically modified nano SiO2。
0.4g of azobisisobutyronitrile, 60g of paraffin oil, 115g of p-chloromethyl styrene and 13g of modified nano SiO were weighed2Stirring uniformly to obtain an oil phase reaction solution; dissolving 5.4g of gelatin and 75g of sodium chloride in 360g of deionized water at 95 ℃, uniformly mixing to obtain water-phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 60 ℃, dropwise adding 0.2g of 1.0 wt% methylene blue ethanol solution, adding 3.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reaction for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO2Chloromethylated styrene complex resin.
Weighing 5g of nano SiO2Adding chloromethylated styrene resin composite into 30g tetrahydrofuran to swell for 4h, adding mixed solution of 15g guanidine hydrochloride and 50g tetrahydrofuran, adding 30g sodium ethoxide ethanol solution with mass fraction of 25 wt%, heating to 85 deg.C, reacting for 8h,filtering, washing with a large amount of deionized water, and vacuum drying at 65 deg.C for 8 hr to obtain nanometer SiO2An anion exchange resin with an inner core.
Measuring the nano SiO2The group conversion rate of the chloromethylation resin compound in the guanidination reaction is 66.8%, the measured strong base exchange capacity of the resin is 3.6mmol/g, the resin is placed in a constant-temperature oil bath at 95 ℃ for heat preservation for 100 hours, the measured loss rate of the strong base exchange capacity of the guanidination resin is 8.1%, and after a pressure resistance test, the ground sphericity rate of the resin is 96.8%.
Example 2
Weighing 100g of nano SiO with particle size of 60nm2Drying in an electrothermal constant-temperature blast drying oven, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2And (5) standby.
Weighing 25g of dried nano SiO2Adding into 600g KH570 ethanol solution with mass fraction of 25 wt%, ultrasonically dispersing for 3h, adjusting pH to 3.8 with oxalic acid, stirring for 6h, centrifuging, washing with 1000g anhydrous ethanol, and vacuum drying at 60 deg.C for 6h to obtain hydrophobically modified nano SiO2。
0.6g of benzoyl peroxide, 70g of toluene, 120g of p-chloromethyl styrene and 15g of modified nano SiO were weighed2Stirring uniformly to obtain an oil phase reaction solution; dissolving 5.6g of gelatin and 78g of sodium chloride in 380g of deionized water at 95 ℃, uniformly mixing to obtain a water-phase reaction solution, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 55 ℃, dropwise adding 0.4g of 1.0 wt% methylene blue ethanol solution, adding 5.0g of divinylbenzene, slowly heating to 95 ℃, stirring for reaction for 14 hours, extracting by using ethanol, drying and screening to obtain the nano SiO2Chloromethylated styrene complex resin.
Weighing 10g of nano SiO2Adding a chloromethylated styrene resin composite into 50g N, N-dimethylformamide to swell for 4h, adding a mixed solution of 20g of guanidine nitrate and 50g N, N-dimethylformamide, adding 60g of a sodium ethoxide ethanol solution with the mass fraction of 25 wt%, heating to 90 ℃, reacting for 8h, filtering, washing with a large amount of deionized water, and drying in vacuum at 70 ℃ for 8h to obtain the nano SiO2Is anion of the inner coreA sub-exchange resin.
Measuring the nano SiO2The group conversion rate of the chloromethylation resin compound in the guanidination reaction is 74.2%, the strong base exchange capacity of the resin is measured to be 3.8mmol/g, the resin is placed in a constant-temperature oil bath at the temperature of 95 ℃ for heat preservation for 100 hours, the loss rate of the strong base exchange capacity of the resin is measured to be 7.4%, and after a pressure-resistant test, the ground sphericity rate of the resin is 97.3%.
Example 3
Weighing 100g of nano SiO with particle size of 80nm2Drying in an electrothermal constant-temperature blast drying oven, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2And (5) standby.
Weighing 25g of dried nano SiO2Adding into 700g KH570 ethanol solution with mass fraction of 20 wt%, ultrasonically dispersing for 4h, adjusting pH to 3.8 with oxalic acid, stirring for reaction for 5h, centrifuging, washing with 1000g anhydrous ethanol, and vacuum drying at 60 deg.C for 6h to obtain hydrophobically modified nano SiO2。
0.6g of potassium persulfate, 60g of gasoline, 110g of p-chloromethyl styrene and 10g of modified nano SiO were weighed2Stirring uniformly to obtain an oil phase reaction solution; dissolving 5g of gelatin and 70g of sodium chloride in 360g of deionized water at 95 ℃, uniformly mixing to obtain a water-phase reaction solution, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 60 ℃, dropwise adding 0.5g of 1.0 wt% methylene blue ethanol solution, adding 8.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reaction for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO2Chloromethylated styrene resin complex.
Weighing 15g of nano SiO2Adding chloromethylated styrene resin composite into 80g dimethyl sulfoxide for swelling for 3.5h, adding 30g guanidine carbonate and 80g dimethyl sulfoxide mixed solution, adding 100g sodium ethoxide ethanol solution with the mass fraction of 25 wt%, heating to 90 ℃, reacting for 8h, filtering, washing with a large amount of deionized water, and vacuum drying at 75 ℃ for 8h to obtain nano SiO2An anion exchange resin with an inner core.
Measuring the nano SiO2Group transfer of chloromethylated resin compound guanidination reactionThe conversion rate is 70.1%, the strong base exchange capacity of the resin is measured to be 3.4mmol/g, the resin is placed in a constant-temperature oil bath at the temperature of 95 ℃ for heat preservation for 100 hours, the loss rate of the strong base exchange capacity of the resin is measured to be 8.2%, and after a pressure resistance test, the ground sphericity rate of the resin is 96.7%.
Example 4
Weighing 100g of nano SiO with particle size of 100nm2Drying in an electrothermal constant-temperature blast drying oven at 200 deg.C for 24 hr, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2And (5) standby.
Weighing 25g of dried nano SiO2Adding into 800g KH570 ethanol solution with mass fraction of 15 wt%, ultrasonically dispersing for 4h, adjusting pH to 3.6 with oxalic acid, stirring for 6h, centrifuging, washing with 1000g anhydrous ethanol, and vacuum drying at 60 deg.C for 6h to obtain hydrophobically modified nano SiO2。
Weighing 0.8g of ammonium persulfate, 50g of paraffin oil, 120g of p-chloromethyl styrene and 15g of modified nano SiO2Stirring uniformly to obtain an oil phase reaction solution; dissolving 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃, uniformly mixing to obtain water-phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 60 ℃, dropwise adding 0.3g of 1.0 wt% methylene blue ethanol solution, adding 4.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reaction for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO2Chloromethylated styrene complex resin.
Weighing 20g of nano SiO2Adding chloromethylated styrene resin composite into 120g tetrahydrofuran to swell for 4h, adding 40g guanidine acetate and 100g tetrahydrofuran mixed solution, adding 150g sodium ethoxide ethanol solution with the mass fraction of 25 wt%, heating to 90 ℃, reacting for 8h, filtering, washing with a large amount of deionized water, and vacuum drying at 70 ℃ for 8h to obtain nano SiO2An anion exchange resin with an inner core.
Measuring the nano SiO2The conversion rate of the group of the chloromethylation resin compound in the guanidine reaction is 66.7 percent, the exchange capacity of the strong base of the resin is measured to be 3.6mmol/g, the resin is placed in a constant temperature oil bath at the temperature of 95 ℃ for heat preservation for 100h, and the measurement is carried outThe loss rate of the strong base exchange capacity of the resin is determined to be 7.6%, and after a pressure resistance test, the ball rate of the resin after grinding is 97.5%.
Comparative example 1
Weighing 0.8g of ammonium persulfate, 50g of paraffin oil and 120g of p-chloromethyl styrene, and uniformly stirring to obtain an oil phase reaction solution; dissolving 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃, uniformly mixing to obtain water-phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 60 ℃, dropwise adding 0.3g of 1.0 wt% methylene blue ethanol solution, adding 4.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reaction for 12 hours, extracting by using ethanol, drying and screening to obtain the chloromethylated styrene resin.
Weighing 20g of chloromethylated styrene resin, adding the chloromethylated styrene resin into 120g of tetrahydrofuran, swelling for 4h, adding a mixed solution of 40g of guanidine acetate and 100g of tetrahydrofuran, adding 150g of a sodium ethoxide ethanol solution with the mass fraction of 25 wt%, heating to 90 ℃, reacting for 8h, filtering, washing with a large amount of deionized water, and drying in vacuum at 70 ℃ for 8h to obtain the chloromethylated guanidino anion exchange resin.
The conversion rate of the group of the guanidination reaction of the chloromethylated resin is measured to be 67.3%, the exchange capacity of strong base of the resin is measured to be 3.6mmol/g, the resin is placed in a constant-temperature oil bath at the temperature of 95 ℃ for heat preservation for 100 hours, the loss rate of the exchange capacity of the strong base of the resin is measured to be 18.9%, and after a pressure-resistant test, the ball rate of the resin after grinding is 80.4%.
Comparative example 2
Weighing 100g of nano SiO with particle size of 100nm2Drying in an electrothermal constant-temperature blast drying oven at 200 deg.C for 24 hr, transferring to a drier, and cooling to room temperature to obtain dried nanometer SiO2And (5) standby.
Weighing 25g of dried nano SiO2Adding into 800g KH570 ethanol solution with mass fraction of 15 wt%, ultrasonically dispersing for 4h, adjusting pH to 3.6 with oxalic acid, stirring for 6h, centrifuging, washing with 1000g anhydrous ethanol, and vacuum drying at 60 deg.C for 6h to obtain hydrophobically modified nano SiO2。
0.8g of ammonium persulfate, 50g of paraffin oil and 120g of p-chloromethyl styrene were weighedAnd 15g of modified nano SiO2Stirring uniformly to obtain an oil phase reaction solution; dissolving 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃, uniformly mixing to obtain water-phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction solution and the water phase reaction solution, heating to 60 deg.C, adding 0.15g 1% methylene blue ethanol solution dropwise, adding 4.0g divinylbenzene, slowly heating to 90 deg.C, stirring for reaction for 12 hr, extracting with ethanol, oven drying, and sieving to obtain nanometer SiO2Chloromethylated styrene complex resin.
Weighing 20g of nano SiO2Adding chloromethylated styrene resin composite into 100g tetrahydrofuran to swell for 4h, adding 20g trimethylamine solution, heating to 90 deg.C, reacting for 8h, filtering, washing with a large amount of deionized water, vacuum drying at 70 deg.C for 8h to obtain nano SiO2An anion exchange resin with an inner core.
The exchange capacity of the strong base of the resin is measured to be 3.4mmol/g, the resin is placed in a constant-temperature oil bath at the temperature of 95 ℃ for heat preservation for 100 hours, the loss rate of the exchange capacity of the strong base of the resin is measured to be 17.8%, and after a pressure resistance test, the round ball rate of the resin after grinding is 84.6%.
The test items related to the invention are as follows: group conversion rate, strong base exchange capacity, heat resistance test and ball rate after grinding.
The test results are summarized in the following table:
table 1 test results of examples and comparative examples:
example KH570 vs. nano SiO2Performing surface hydrophobic modification to obtain KH570 coupled nano SiO2Then suspension polymerizing with p-chloromethyl styrene to obtain nano SiO2Polystyrene chloromethylation composite resin is reacted with guanidine salt to prepare nano SiO2Anion exchange for the coreAnd (3) resin. Comparative example 1 suspension polymerization of chloromethylstyrene, reaction with guanidinium salt to give anion exchange resin, without addition of KH570 to couple SiO nanoparticles2The anion exchange resin prepared in the example has better heat resistance and better sphericity ratio after grinding than the anion exchange resin prepared in the comparative example 1. Comparative example 2 coupling of nano SiO with KH5702Suspension polymerization with p-chloromethyl styrene to obtain nano SiO2The polystyrene chloromethylation composite resin is reacted with trimethylamine to prepare anion exchange resin, guanidine salt is not added for amination, the heat resistance test result of the anion exchange resin prepared in the embodiment is obviously superior to that of the comparative example 2, and the sphericity rate after grinding is also higher than that of the comparative example 2.
Referring to FIG. 1, the embodiment of the present invention uses nano SiO2Preparing process flow of anion exchange resin with inner core;
referring to FIG. 2, the nano SiO prepared in example 1 of the present invention2The anion exchange resin as the inner core is in a microspherical shape.
Referring to FIG. 3, the nano SiO prepared in example 2 of the present invention2The anion exchange resin as the inner core is in a microspherical shape.
In summary, although the present invention has been described in detail with reference to the specific embodiments, the description is illustrative, and those skilled in the art can make various modifications and changes based on the principle without departing from the invention, and the scope of the invention is defined by the appended claims.
Claims (8)
1. With nano SiO2The anion exchange resin as the kernel is characterized in that the resin is a compound of organic polymer and inorganic material with a core-shell structure, and the kernel is nano SiO2And the shell is chloromethylated styrene resin.
2. A nano SiO as claimed in claim 12The preparation method of the anion exchange resin with the inner core is characterized by comprising the following steps:
step a) preparing nano SiO2Drying to obtain dry nano SiO2；
Step b) drying the nano SiO obtained in step a)2Adding the mixture into a hydrophobic modifier solution, adjusting the pH value of a system to 3.4-4.0 by using oxalic acid after ultrasonic dispersion for 2-4 h, stirring and reacting for 4-8 h, centrifugally separating, washing by using absolute ethyl alcohol, and drying in vacuum for 6-8 h at the temperature of 60-80 ℃ to obtain the hydrophobic modified nano SiO2；
Step c), mixing the components in a mass ratio of 0.2-1: 120-180: 220-450: 25-60 of initiator, pore-forming agent, p-chloromethyl styrene and the hydrophobic modified nano SiO obtained in step b)2Stirring uniformly to obtain an oil phase reaction solution; and then, mixing the raw materials in a mass ratio of 1-2: 20-25: uniformly mixing 100-150 parts of gelatin, sodium chloride and deionized water to obtain a water-phase reaction solution, and cooling to 40-50 ℃; mixing the components in a mass ratio of 1: 2-1: 2.5 mixing the oil-phase reaction liquid with the water-phase reaction liquid; heating to 50-60 ℃, wherein the mass ratio of the dropwise addition to the oil phase reaction liquid is 0.001-0.003: 1 is 1.0 wt% of methylene blue ethanol solution, and the mass ratio of the added materials to p-chloromethyl styrene is 0.02: 1-0.1: 1, slowly heating to 90-95 ℃, stirring for reaction for 12-24 hours, extracting by using ethanol, drying and screening to obtain nano SiO2Chloromethylated styrene resin complex;
step d) mixing the nano SiO in step c)2Adding a chloromethylated styrene resin composite into a solvent for swelling for 2-4 h, adding guanidinium dissolved in the solvent in advance, adding a sodium ethoxide ethanol solution, heating to 80-100 ℃, reacting for 4-8 h, filtering, washing with a large amount of deionized water, and vacuum drying at 60-80 ℃ for 8-12 h to obtain the nano SiO2An anion exchange resin with an inner core.
3. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the nano SiO in the step a) is2The particle size range of 30-100 nm, and the drying method comprises the following steps: mixing nano SiO2Drying in a constant temperature air-blast drying oven, transferring to a drier, and cooling to room temperature to obtainDried nano SiO2。
4. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the hydrophobic modifier solution in the step b) adopts a KH570 ethanol solution with the mass fraction of 15-25 wt%, and the hydrophobic modifier solution and the nano SiO2The mass ratio of (A) to (B) is 20: 1-40: 1, the dosage of ethanol used in washing is 30-50 times of the mass of the hydrophobic modifier solution.
5. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the initiator in the step c) is one of azodiisobutyronitrile, benzoyl peroxide, ammonium persulfate and potassium persulfate, and the pore-forming agent is one of paraffin oil, gasoline and toluene.
6. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the swelling agent in the step d) is one of N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) and Tetrahydrofuran (THF).
7. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the guanidine salt in the step d) is one of guanidine hydrochloride, guanidine carbonate, guanidine acetate and guanidine nitrate.
8. The method of claim 2 wherein the SiO is a nano-scale SiO2The preparation method of the anion exchange resin with the inner core is characterized in that the guanidine salt and the nano SiO in the step d) are prepared2The mass ratio of the chloromethylated styrene resin composite is 1.5: 1-5: 1, and the mass of the solvent is equal to that of the nano SiO2The mass ratio of the chloromethylated styrene resin compound is 5-10: 1, the concentration of the sodium ethoxide ethanol solution is 20-30 wt%, and the mass ratio of the sodium ethoxide ethanol solution to the guanidine salt is 2: 1-5: 1.
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