CN113698554B - Nano SiO2Anion exchange resin as core and preparation method thereof - Google Patents
Nano SiO2Anion exchange resin as core and preparation method thereof Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 116
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 150000003440 styrenes Chemical class 0.000 claims abstract description 18
- 150000002357 guanidines Chemical class 0.000 claims abstract description 14
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 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 85
- 239000012295 chemical reaction liquid Substances 0.000 claims description 32
- 239000012071 phase Substances 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003921 oil Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000007265 chloromethylation reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- 239000008346 aqueous phase Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 9
- 108010010803 Gelatin Proteins 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
- 239000003607 modifier Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000005662 Paraffin oil Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 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
- 230000008961 swelling Effects 0.000 claims description 4
- 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 3
- 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
- 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
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 15
- 239000004793 Polystyrene Substances 0.000 abstract description 9
- 229920002223 polystyrene Polymers 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 5
- 239000000805 composite resin Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004042 decolorization 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
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000002585 base Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 12
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- -1 quaternary ammonium ions Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 7
- 229960004198 guanidine Drugs 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 4
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004321 preservation Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 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
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses an anion exchange resin with nano SiO 2 as an inner core and a preparation method thereof, wherein the anion exchange resin is an organic polymer and inorganic material compound with a core-shell structure, the inner core is nano SiO 2, and the outer shell is chloromethylated styrene resin. According to the preparation method of the anion exchange resin, KH570 is utilized to carry out surface hydrophobic modification on nano SiO 2 to obtain KH570 coupled nano SiO 2, then nano SiO 2 polystyrene chloromethylated composite resin is obtained by suspension polymerization of the nano SiO 2 and p-chloromethylstyrene, and the anion exchange resin is prepared by reaction with guanidine salt. 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 fine treatment of air cooling units of thermal power plants, drug intermediate decolorization, industrial wastewater impurity ion removal and the like under high temperature environments.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to anion exchange resin with nano SiO 2 as a core and a preparation method thereof.
Background
The polystyrene anion exchange resin is widely used in the fields of organic catalytic reaction, condensate fine treatment of air cooling units of thermal power plants, decolorization of medicine intermediates, removal of impurity ions in industrial wastewater and the like. However, the commercial strong-base anion exchange resin of the OH - type has the structure containing hydroxyl benzyl trialkyl ammonium, namely quaternary ammonium groups, when the use temperature exceeds 60 ℃, the quaternary ammonium groups of the quaternary ammonium strong-base resin can undergo Hoffman degradation reaction, so that the quaternary ammonium groups fall off or are converted into weak base groups from the strong base groups, the strong base anion exchange resin is deactivated, the structural strength of the resin is deteriorated, and the exchange capacity is reduced, thereby limiting the use range of the resin.
Research work to improve the heat resistance of polystyrene strong base anion exchange resins has been receiving attention from researchers in various countries. The bond energy of the quaternary ammonium ions is enhanced by adopting measures, the decomposition activation energy of the quaternary ammonium ions is improved, and the method is an effective way for achieving the aim of improving the thermal stability of the polystyrene strong base anion exchange resin, and mainly comprises the following 3 ways: (1) Changing the hydrocarbyl R 1、R2、R3 group attached to the quaternary ammonium nitrogen atom; (2) Changing the electron effect of benzene ring (introducing electron-withdrawing substituent or electron-donating substituent) to raise the activation energy of C-N bond between methylene and nitrogen atom connected with benzene ring, so as to make it more stable; (3) The methylene between benzene ring and quaternary ammonium salt group is changed into long-chain alkyl, thus obtaining the novel polystyrene strong base anion exchange resin. Japanese mitsubishi chemical company developed a strongly basic anion exchange resin with a long carbon chain spacer structure, improving the thermal stability of the resin by introducing long carbon chain spacers in the benzene ring and quaternary nitrogen atoms of the resin. Through different synthesis paths, china Chen Qun, wang, liu Yingchun and the like, strong base anion exchange resins with long spacer arms are also synthesized, and the thermal stability of the resins is greatly improved. From the current research situation, the structural modification research of the strong base anion exchange resin is mainly to change the connection mode of the quaternary ammonium group and the resin skeleton, and is limited by the quaternary ammonium group structure, so that the thermal stability of the resin is not improved at all, and most importantly, the synthetic 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 alkalinity equivalent to NaOH, three nitrogen atoms in self cations are symmetrically distributed around carbon atoms, and the thermal stability of the guanidine compound is high due to the conjugation effect. The application of the modified polyamide resin to the ion exchange resin can obviously improve the temperature resistance of the anion exchange resin. Patent CN201110109696.8 discloses a high temperature resistant guanidino strong base anion exchange resin and a synthesis method thereof. The preparation of the resin mainly utilizes the chemical reaction between chloromethyl and free guanidine on the skeleton of chloromethyl polystyrene resin. However, the preparation process of the guanidine resin uses extremely unstable free guanidine, which increases the preparation difficulty, and the conversion rate of chemical bonding reaction between guanidine and chloromethyl in the synthesis process is low. The patent CN109180851.6 discloses another preparation method of high-temperature resistant guanidino alkali resin, which utilizes KH570 to carry out surface hydrophobic modification on face cubic phase delta-Bi 2O3 synthesized by a microwave method, prepares delta-Bi 2O3 resin white sphere core-shell compound through suspension polymerization, and then reacts with guanidine hydrochloride after chloromethylation reaction to prepare the high-temperature resistant guanidino alkali resin. However, the face-cubic phase delta-Bi 2O3 synthesized by the microwave method is not easy to obtain, the microwave method is essentially used for replacing a hydrothermal method, the depth of the microwave penetrating through a medium is limited, the microwave is harmful to human bodies, the microwave is not suitable for large-scale application, in addition, the chloromethylation process of the white balls cannot be controlled in a directional manner, the number of chloromethyl introduced sites are not controlled, and the final alkali exchange amount is affected.
Therefore, the chloromethylated styrene resin compound obtained by carrying out hydrophobic modification on the nano material SiO 2 which is industrially produced on a large scale and is most widely applied at present and directly and quantitatively polymerizing the p-chloromethyl styrene monomer is reacted with guanidine salt to obtain the anion exchange resin taking nano SiO 2 as the core, so that the synthetic 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 commercial quaternary ammonium anion exchange resin, the production process and the production cost are not obviously changed, and the method has important significance for industrial production and application.
Disclosure of Invention
The invention provides an anion exchange resin with nano SiO 2 as an inner core and a preparation method thereof, and the anion exchange resin has good temperature resistance, and compared with the existing method, the synthetic process of the resin is simple, and the obtained resin has high conversion rate, controllable strong alkali exchange capacity, strong heat resistance stability and high structural strength.
In order to solve the technical problems, the invention adopts the following technical scheme:
An anion exchange resin with nano SiO 2 as kernel is prepared from organic high-molecular and inorganic material through proportionally mixing, nano SiO 2 as kernel, and chloromethylation styrene as shell.
The preparation method of the anion exchange resin with the nano SiO 2 as the core comprises the following steps:
Step a), drying the nano SiO 2 to obtain dried nano SiO 2;
Step b), adding the dried nano SiO 2 obtained in the step a) into a hydrophobic modifier solution, performing ultrasonic dispersion for 2-4 hours, regulating the pH value of a system to 3.4-4.0 by oxalic acid, stirring for reaction for 4-8 hours, performing centrifugal separation, washing by absolute ethyl alcohol, and performing vacuum drying at 60-80 ℃ for 6-8 hours to obtain hydrophobic modified nano SiO 2;
step c) the mass ratio is 0.2-1: 120-180: 220-450: 25-60 of initiator, pore-forming agent, p-chloromethyl styrene and the hydrophobic modified nano SiO 2 obtained in the step b) are uniformly stirred to obtain oil phase reaction liquid; and then the mass ratio is 1-2: 20-25: uniformly mixing gelatin, sodium chloride and deionized water of 100-150 to obtain aqueous phase reaction liquid, and cooling to 40-50 ℃; the mass ratio is 1: 2-1: 2.5 mixing the oil phase reaction liquid with the water phase reaction liquid; heating to 50-60 ℃, dropwise adding a methylene blue ethanol solution with the mass ratio of 0.001-0.003:1 to the oil phase reaction liquid of 1.0wt%, and adding a methyl styrene-p-chloride with the mass ratio of 0.02:1 to 0.1:1, slowly heating to 90-95 ℃, stirring and reacting for 12-24 hours, extracting with ethanol, drying and screening to obtain a nano SiO 2 chloromethylated styrene resin compound;
Step d), adding the nano SiO 2 chloromethylated styrene resin compound in the step c) into a solvent to swell for 2-4 hours, adding guanidine salt which is dissolved in the solvent in advance, adding sodium ethoxide ethanol solution, heating to 80-100 ℃, reacting for 4-8 hours, filtering, washing with a large amount of deionized water, and vacuum drying at 60-80 ℃ for 8-12 hours to obtain the anion exchange resin taking nano SiO 2 as the core.
The particle size range of the nano SiO 2 in the step a) is 30-100 nm, and the drying method is as follows: and (3) placing the nano SiO 2 in a constant temperature blast drying oven for drying, transferring to a dryer for cooling to room temperature, and obtaining the dried nano SiO 2.
The hydrophobic modifier solution in the step b) is KH570 ethanol solution with the mass fraction of 15-25 wt%, and the mass ratio of the hydrophobic modifier solution to nano SiO 2 is 20: 1-40: 1, the ethanol consumption used in the washing process is 30-50 times of the mass of the hydrophobic modifier solution.
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.
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.
The mass ratio of the guanidine salt to the nano SiO 2 chloromethylated styrene resin compound in the step d) is 1.5:1-5:1, and the mass ratio of the solvent to the nano SiO 2 chloromethylated styrene resin compound is 5-10: 1, the concentration of the sodium ethoxide ethanol solution is 20-30wt%, and the mass ratio of the sodium ethoxide ethanol solution to the guanidine salt is 2:1 to 5:1.
The beneficial effects of the invention are as follows:
Compared with the prior art, the invention introduces the nano material SiO 2 which is industrially produced on a large scale and is most widely applied at present into the polystyrene ion exchange resin, firstly, the introduction of the nano SiO 2 realizes the molecular-level compounding of the organic polymer material and the inorganic material, the structural strength of the resin is enhanced, secondly, the introduction of the nano SiO 2 with different nano sizes has the regulation and control function on the particle size of the resin, and secondly, the excellent heat resistance of the nano SiO 2 can improve the heat stability of the ion exchange resin. In addition, the chloromethyl styrene monomer and the hydrophobically modified nano SiO 2 are directly used for quantitative polymerization to obtain a chloromethylation resin compound with a core-shell structure, and then the chloromethylation resin compound reacts with guanidine salt to obtain the anion exchange resin taking nano SiO 2 as an inner core. The anion exchange resin has potential application prospect in the fields of organic catalytic reaction, fine treatment of condensate water of air cooling units of thermal power plants, decolorization of drug intermediates, removal of impurity ions in industrial wastewater and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing anion exchange resin with nano SiO 2 as a core according to an embodiment of the present invention;
FIG. 2 is a graph showing the morphology of an anion exchange resin with a nano SiO 2 core prepared in example 1 of the present invention
FIG. 3 is a graph showing the morphology of an anion exchange resin with nano SiO 2 as the core prepared in example 2 of the present invention
Detailed Description
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Example 1
100G of nano SiO 2 with the particle size of 30nm is weighed and placed in an electrothermal constant temperature blast drying oven to be dried, and then transferred to a dryer to be cooled to room temperature, thus obtaining the dried nano SiO 2 for standby.
Weighing 20g of dried nano SiO 2, adding into 500g of KH570 ethanol solution with mass fraction of 20wt%, performing ultrasonic dispersion for 2h, adjusting pH value of the system to 3.5 with oxalic acid, stirring for reaction for 5h, performing centrifugal separation, washing with 800g of absolute ethanol, and vacuum drying at 60 ℃ for 6h to obtain the hydrophobic modified nano SiO 2.
Weighing 0.4g of azodiisobutyronitrile, 60g of paraffin oil, 115g of p-chloromethyl styrene and 13g of modified nano SiO 2, and uniformly stirring to obtain an oil phase reaction liquid; then 5.4g of gelatin and 75g of sodium chloride are dissolved and mixed uniformly in 360g of deionized water at 95 ℃ to obtain aqueous phase reaction liquid, and the aqueous phase reaction liquid is cooled to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 60 ℃, dropwise adding 0.2g of 1.0wt% methylene blue ethanol solution, adding 3.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reacting for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO 2 chloromethylated styrene compound resin.
5G of nano SiO 2 chloromethylated styrene resin compound is weighed, added into 30g of tetrahydrofuran for swelling for 4 hours, added with a mixed solution of 15g of guanidine hydrochloride and 50g of tetrahydrofuran, added with 30g of 25wt% sodium ethoxide ethanol solution, heated to 85 ℃, reacted for 8 hours, filtered, washed with a large amount of deionized water, and dried in vacuum for 8 hours at 65 ℃ to obtain the anion exchange resin taking nano SiO 2 as the core.
The radical conversion rate of the nano SiO 2 chloromethylation resin compound guanylate reaction is 66.8%, the alkali exchange amount of the resin is 3.6mmol/g, the resin is placed in a constant temperature oil bath at 95 ℃ for heat preservation for 100h, the alkali exchange amount loss rate of the guanidine resin is 8.1%, and after pressure resistance test, the ball rate of the resin after grinding is 96.8%.
Example 2
100G of nano SiO 2 with the particle size of 60nm is weighed and placed in an electrothermal constant temperature blast drying oven to be dried, and then transferred to a dryer to be cooled to room temperature, thus obtaining the dried nano SiO 2 for standby.
Weighing 25g of dried nano SiO 2, adding into 600g of KH570 ethanol solution with mass fraction of 25wt%, performing ultrasonic dispersion for 3h, adjusting pH value of the system to 3.8 with oxalic acid, stirring for reaction for 6h, performing centrifugal separation, washing with 1000g of absolute ethanol, and vacuum drying at 60 ℃ for 6h to obtain the hydrophobic modified nano SiO 2.
Weighing 0.6g of benzoyl peroxide, 70g of toluene, 120g of p-chloromethyl styrene and 15g of modified nano SiO 2, and uniformly stirring to obtain an oil phase reaction liquid; dissolving 5.6g of gelatin and 78g of sodium chloride in 380g of deionized water at 95 ℃ and uniformly mixing to obtain aqueous phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 55 ℃, dropwise adding 0.4g of 1.0wt% methylene blue ethanol solution, adding 5.0g of divinylbenzene, slowly heating to 95 ℃, stirring for reacting for 14 hours, extracting by using ethanol, drying and screening to obtain the nano SiO 2 chloromethylated styrene compound resin.
10G of nano SiO 2 chloromethylated styrene resin compound is weighed and added into 50g of N, N-dimethylformamide to be swelled for 4 hours, 20g of guanidine nitrate and 50g of N, N-dimethylformamide mixed solution are added, 60g of 25wt% sodium ethoxide ethanol solution is added, the temperature is raised to 90 ℃, the reaction is carried out for 8 hours, filtration is carried out, a large amount of deionized water is used for washing, and vacuum drying is carried out for 8 hours at 70 ℃ to obtain the anion exchange resin taking nano SiO 2 as the inner core.
The radical conversion rate of the nano SiO 2 chloromethylation resin compound guanylation reaction is measured to be 74.2%, the alkali exchange amount of the resin is measured to be 3.8mmol/g, the resin is placed in a constant temperature oil bath at 95 ℃ for heat preservation for 100h, the alkali exchange amount loss rate of the resin is measured to be 7.4%, and after a pressure-resistant test, the ball rate of the resin after grinding is 97.3%.
Example 3
100G of nano SiO 2 with the particle size of 80nm is weighed and placed in an electrothermal constant temperature blast drying oven to be dried, and then transferred to a dryer to be cooled to room temperature, thus obtaining the dried nano SiO 2 for standby.
Weighing 25g of dried nano SiO 2, adding into 700g of KH570 ethanol solution with mass fraction of 20wt%, performing ultrasonic dispersion for 4 hours, adjusting the pH value of the system to 3.8 by oxalic acid, stirring for reaction for 5 hours, performing centrifugal separation, washing by 1000g of absolute ethanol, and performing vacuum drying at 60 ℃ for 6 hours to obtain the hydrophobic modified nano SiO 2.
Weighing 0.6g of potassium persulfate, 60g of gasoline, 110g of p-chloromethyl styrene and 10g of modified nano SiO 2, and uniformly stirring to obtain an oil phase reaction solution; then 5g of gelatin and 70g of sodium chloride are dissolved and mixed uniformly in 360g of deionized water at 95 ℃ to obtain aqueous phase reaction liquid, and the aqueous phase reaction liquid is cooled to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 60 ℃, dropwise adding 0.5g of 1.0wt% methylene blue ethanol solution, adding 8.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reacting for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO 2 chloromethylated styrene resin compound.
15G of nano SiO 2 chloromethylated styrene resin compound is weighed, added into 80g of dimethyl sulfoxide to be swelled for 3.5h, 30g of guanidine carbonate and 80g of dimethyl sulfoxide mixed solution are added, 100g of 25wt% sodium ethoxide ethanol solution is added, the temperature is raised to 90 ℃, the reaction is carried out for 8h, the filtration is carried out, the washing is carried out by a large amount of deionized water, and the vacuum drying is carried out for 8h at 75 ℃ to obtain the anion exchange resin taking nano SiO 2 as the inner core.
The radical conversion rate of the nano SiO 2 chloromethylation resin compound guanylation reaction is 70.1%, the alkali exchange amount of the resin is 3.4mmol/g, the resin is placed in a constant temperature oil bath at 95 ℃ for heat preservation for 100h, the alkali exchange amount loss rate of the resin is 8.2%, and after pressure resistance test, the ball rate of the resin after grinding is 96.7%.
Example 4
100G of nano SiO 2 with the grain diameter of 100nm is weighed and placed in a 200 ℃ electrothermal constant temperature blast drying oven to be dried for 24 hours, and then transferred to a dryer to be cooled to room temperature, thus obtaining the dried nano SiO 2 for standby.
Weighing 25g of dried nano SiO 2, adding into 800g of KH570 ethanol solution with mass fraction of 15wt%, performing ultrasonic dispersion for 4 hours, adjusting the pH value of the system to 3.6 by oxalic acid, stirring for reaction for 6 hours, performing centrifugal separation, washing by 1000g of absolute ethanol, and performing vacuum drying at 60 ℃ for 6 hours to obtain the hydrophobic modified nano SiO 2.
Weighing 0.8g of ammonium persulfate, 50g of paraffin oil, 120g of p-chloromethyl styrene and 15g of modified nano SiO 2, and uniformly stirring to obtain an oil phase reaction solution; dissolving and uniformly mixing 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃ to obtain aqueous phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 60 ℃, dropwise adding 0.3g of 1.0wt% methylene blue ethanol solution, adding 4.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reacting for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO 2 chloromethylated styrene compound resin.
Weighing 20g of nano SiO 2 chloromethylated styrene resin compound, adding the nano SiO 2 chloromethylated styrene resin compound into 120g of tetrahydrofuran for swelling for 4 hours, adding 40g of guanidine acetate and 100g of tetrahydrofuran mixed solution, adding 150g of 25wt% sodium ethoxide ethanol solution, heating to 90 ℃, reacting for 8 hours, filtering, washing with a large amount of deionized water, and vacuum drying at 70 ℃ for 8 hours to obtain the anion exchange resin taking nano SiO 2 as the core.
The radical conversion rate of the nano SiO 2 chloromethylation resin compound guanylation reaction is 66.7%, the alkali exchange amount of the resin is 3.6mmol/g, the resin is placed in a constant temperature oil bath at 95 ℃ for heat preservation for 100h, the alkali exchange amount loss rate of the resin is 7.6%, and after 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 and uniformly mixing 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃ to obtain aqueous phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 60 ℃, dropwise adding 0.3g of 1.0wt% methylene blue ethanol solution, adding 4.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reacting for 12 hours, extracting by using ethanol, drying and screening to obtain chloromethylated styrene resin.
20G of chloromethylation styrene resin is weighed and added into 120g of tetrahydrofuran to be swelled for 4 hours, 40g of guanidine acetate and 100g of tetrahydrofuran mixed solution are added, 150g of sodium ethoxide ethanol solution with the mass fraction of 25wt% is added, the temperature is raised to 90 ℃, the reaction is carried out for 8 hours, filtration is carried out, a large amount of deionized water is used for washing, and vacuum drying is carried out for 8 hours at 70 ℃ to obtain chloromethylation guanidino anion exchange resin.
The radical conversion rate of the guanylation reaction of the chloromethylation resin was measured to be 67.3%, the alkali exchange amount of the resin was measured to be 3.6mmol/g, the resin was placed in a constant temperature oil bath at 95 ℃ and kept for 100 hours, the alkali exchange amount loss rate of the resin was measured to be 18.9%, and after the pressure-resistant test, the ball rate after grinding of the resin was 80.4%.
Comparative example 2
100G of nano SiO 2 with the grain diameter of 100nm is weighed and placed in a 200 ℃ electrothermal constant temperature blast drying oven to be dried for 24 hours, and then transferred to a dryer to be cooled to room temperature, thus obtaining the dried nano SiO 2 for standby.
Weighing 25g of dried nano SiO 2, adding into 800g of KH570 ethanol solution with mass fraction of 15wt%, performing ultrasonic dispersion for 4 hours, adjusting the pH value of the system to 3.6 by oxalic acid, stirring for reaction for 6 hours, performing centrifugal separation, washing by 1000g of absolute ethanol, and performing vacuum drying at 60 ℃ for 6 hours to obtain the hydrophobic modified nano SiO 2.
Weighing 0.8g of ammonium persulfate, 50g of paraffin oil, 120g of p-chloromethyl styrene and 15g of modified nano SiO 2, and uniformly stirring to obtain an oil phase reaction solution; dissolving and uniformly mixing 6g of gelatin and 75g of sodium chloride in 380g of deionized water at 95 ℃ to obtain aqueous phase reaction liquid, and cooling to 50 ℃; mixing the oil phase reaction liquid and the water phase reaction liquid, heating to 60 ℃, dropwise adding 0.15g of 1% methylene blue ethanol solution, adding 4.0g of divinylbenzene, slowly heating to 90 ℃, stirring for reacting for 12 hours, extracting by using ethanol, drying and screening to obtain the nano SiO 2 chloromethylated styrene compound resin.
Weighing 20g of nano SiO 2 chloromethylated styrene resin compound, adding into 100g of tetrahydrofuran to swell for 4 hours, adding into 20g of trimethylamine solution, heating to 90 ℃, reacting for 8 hours, filtering, washing with a large amount of deionized water, and vacuum drying at 70 ℃ for 8 hours to obtain the anion exchange resin taking nano SiO 2 as the core.
The resin was measured to have a strong base exchange capacity of 3.4mmol/g, and the resin was kept in a constant temperature oil bath at 95℃for 100 hours, and the resin was measured to have a strong base exchange capacity loss rate of 17.8% and a ball rate after grinding of 84.6% after a pressure test.
The test items related to the invention are: group conversion, strong base exchange capacity, heat resistance test, ball after grinding.
The test results are summarized in the following table:
Table 1 test results for examples and comparative examples:
According to the embodiment, KH570 is adopted to carry out surface hydrophobic modification on nano SiO 2 to obtain KH570 coupled nano SiO 2, then nano SiO 2 polystyrene chloromethylation composite resin is obtained by suspension polymerization of the nano SiO 2 and p-chloromethyl styrene, and anion exchange resin with nano SiO 2 as an inner core is prepared by reaction of the nano SiO 2 polystyrene chloromethylation composite resin and guanidine salt. In comparative example 1, anion exchange resin is prepared by suspension polymerization of chloromethyl styrene and reaction with guanidine salt, KH570 is not added to couple nano SiO 2, and the heat resistance and ball rate after grinding of the anion exchange resin prepared in the example are obviously better than those of comparative example 1. In comparative example 2, KH570 is adopted to couple nano SiO 2, nano SiO 2 polystyrene chloromethylation composite resin is obtained by suspension polymerization of the nano SiO 2 and p-chloromethyl styrene, anion exchange resin is obtained by reaction with trimethylamine, guanidine salt is not added for amination, the heat resistance test result of the anion exchange resin prepared in the example is obviously superior to that of comparative example 2, and the ball rate after grinding is also higher than that of comparative example 2.
Referring to fig. 1, the preparation process of the anion exchange resin with nano SiO 2 as the core in the embodiment of the invention is as follows;
Referring to fig. 2, the anion exchange resin with nano SiO 2 as the core prepared in example 1 of the present invention has a microsphere morphology.
Referring to fig. 3, the anion exchange resin with nano SiO 2 as the core prepared in embodiment 2 of the present invention has a microsphere shape.
In general, although the invention has been described in detail with reference to specific embodiments thereof, the description is illustrative, and various modifications and changes can be made therein by those skilled in the art without departing from the principles of the invention, which fall within the scope of the invention as defined in the appended claims.
Claims (6)
1. The preparation method of anion exchange resin with nano SiO 2 as kernel is characterized in that the resin is organic polymer and inorganic material compound with core-shell structure, the kernel is nano SiO 2, and the shell is chloromethylation styrene resin;
The preparation method comprises the following steps:
Step a), drying the nano SiO 2 to obtain dried nano SiO 2;
Step b), adding the dried nano SiO 2 obtained in the step a) into a hydrophobic modifier solution, performing ultrasonic dispersion for 2-4 hours, regulating the pH value of a system to 3.4-4.0 by oxalic acid, stirring for reaction for 4-8 hours, performing centrifugal separation, washing by absolute ethyl alcohol, and performing vacuum drying at 60-80 ℃ for 6-8 hours to obtain hydrophobic modified nano SiO 2;
Step c) the mass ratio is 0.2-1: 120-180: 220-450: 25-60 of initiator, pore-forming agent, p-chloromethyl styrene and the hydrophobic modified nano SiO 2 obtained in the step b) are uniformly stirred to obtain oil phase reaction liquid; and then the mass ratio is 1-2: 20-25: uniformly mixing gelatin, sodium chloride and deionized water of 100-150 to obtain aqueous phase reaction liquid, and cooling to 40-50 ℃; the mass ratio is 1: 2-1: 2.5 mixing the oil phase reaction liquid with the water phase reaction liquid; heating to 50-60 ℃, and dropwise adding the mixture with the oil phase reaction liquid in a mass ratio of 0.001-0.003: 1 is 1.0 weight percent of methylene blue ethanol solution, and the mass ratio of the methylene blue ethanol solution to the p-chloromethyl styrene is 0.02:1 to 0.1:1, slowly heating to 90-95 ℃, stirring and reacting for 12-24 hours, extracting with ethanol, drying and screening to obtain a nano SiO 2 chloromethylated styrene resin compound;
Step d), adding the nano SiO 2 chloromethylated styrene resin compound in the step c) into a solvent to swell for 2-4 hours, adding guanidine salt which is dissolved in the solvent in advance, adding sodium ethoxide ethanol solution, heating to 80-100 ℃, reacting for 4-8 hours, filtering, washing with a large amount of deionized water, and vacuum drying at 60-80 ℃ for 8-12 hours to obtain anion exchange resin taking nano SiO 2 as an inner core;
the grain diameter range of the nano SiO 2 in the step a) is 30-100 nm;
the hydrophobic modifier solution in the step b) adopts KH570 ethanol solution with the mass fraction of 15-25 wt%;
The mass ratio of the guanidine salt to the nano SiO 2 chloromethylated styrene resin compound in the step d) is 1.5:1-5:1, and the mass ratio of the solvent to the nano SiO 2 chloromethylated styrene resin compound is 5-10: 1, the concentration of the sodium ethoxide ethanol solution is 20-30wt%, and the mass ratio of the sodium ethoxide ethanol solution to the guanidine salt is 2:1 to 5:1.
2. The method for preparing anion exchange resin with nano SiO 2 as core according to claim 1, wherein the drying method in step a) is: and (3) placing the nano SiO 2 in a constant temperature blast drying oven for drying, transferring to a dryer for cooling to room temperature, and obtaining the dried nano SiO 2.
3. The method for preparing anion exchange resin with nano SiO 2 as core according to claim 1, wherein the mass ratio of the hydrophobic modifier solution to nano SiO 2 in the step b) is 20: 1-40: 1, the ethanol consumption in washing is 30-50 times of the mass of the hydrophobic modifier solution.
4. The method for preparing anion exchange resin with nano SiO 2 as core according to claim 1, wherein 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.
5. The method for preparing anion exchange resin with nano SiO 2 as core according to claim 1, wherein the swelling agent in the step d) is one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and Tetrahydrofuran (THF).
6. The method for preparing anion exchange resin with nano SiO 2 as core as set forth in claim 1, wherein the guanidine salt in the step d) is one of guanidine hydrochloride, guanidine carbonate, guanidine acetate and guanidine nitrate.
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