CN112592427B - Macroporous adsorption resin and preparation method thereof - Google Patents
Macroporous adsorption resin and preparation method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 title abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 30
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 108010010803 Gelatin Proteins 0.000 claims abstract description 21
- 229920000159 gelatin Polymers 0.000 claims abstract description 21
- 239000008273 gelatin Substances 0.000 claims abstract description 21
- 235000019322 gelatine Nutrition 0.000 claims abstract description 21
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 21
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 13
- 150000002978 peroxides Chemical class 0.000 claims abstract description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 31
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 26
- GNVCMJDQDGNTRM-ZSCHJXSPSA-M (2S)-2,6-diaminohexanoate tetrabutylazanium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC.C(CCN)C[C@@H](C(=O)[O-])N GNVCMJDQDGNTRM-ZSCHJXSPSA-M 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004472 Lysine Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003361 porogen Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 208000005374 Poisoning Diseases 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 231100000419 toxicity Toxicity 0.000 description 12
- 230000001988 toxicity Effects 0.000 description 12
- 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 description 10
- 238000012360 testing method Methods 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 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 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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Abstract
The invention provides a macroporous adsorption resin which is prepared from the following raw materials in parts by weight: 950-1050 parts of pure water, 4-6 parts of gelatin, 0.4-0.6 part of methylene blue, 90-110 parts of methyl acrylate, 9-11 parts of triallyl isocyanurate, 7-9 parts of divinylbenzene, 45-55 parts of pore-foaming agent and 1-2 parts of peroxide. The invention also provides a preparation method of the macroporous adsorption resin. The macroporous adsorption resin provided by the invention has low toxicity, and can effectively reduce the poisoning risk of production personnel.
Description
Technical Field
The invention relates to a resin, in particular to a macroporous adsorption resin and a preparation method thereof.
Background
The macroporous adsorption resin is a macromolecular adsorption resin which does not contain exchange groups and has a macroporous structure, has a good macroporous network structure and a larger specific surface area, can selectively adsorb organic matters in an aqueous solution through physics, is a novel organic polymer adsorbent developed in the 60 th century, and has been widely applied to the fields of environmental protection, food, medicine and the like. The macroporous adsorption resin is generally white spherical particles, has stable physicochemical properties, is insoluble in acid, alkali and organic solvents, and is not influenced by inorganic salts and strong ion low molecular compounds.
The macroporous adsorption resin is generally prepared by mainly using styrene, acrylic ester, divinylbenzene and the like as raw materials and adding a certain proportion of pore-foaming agents into a gelatin solution for polymerization, wherein the styrene is a polymerization monomer, the divinylbenzene is a cross-linking agent, the toluene, the xylene, the gasoline and the like are used as the pore-foaming agents, and the pore-foaming agents are mutually cross-linked and polymerized to form a porous skeleton structure of the macroporous adsorption resin. At present, toluene, xylene, gasoline and the like are mostly used as pore-foaming agents in the preparation process of macroporous adsorption resin, and although a good pore-foaming effect can be achieved, the pore-foaming agents have certain toxicity, so that production personnel have a poisoning risk in the production process, and products also have certain toxicity.
Chinese patent application CN201410598735.9 discloses a "preparation method of macroporous adsorption resin", said method comprises the following steps: 1) taking ethylene-vinyl acetate, methacrylonitrile and styrene as monomers, taking toluene and xylene as mixed pore-foaming agents, taking benzoyl peroxide and azodiisobutyronitrile as mixed initiators, and mixing to obtain an oil phase; 2) dissolving polyvinyl alcohol, gelatin and sodium chloride in deionized water, and stirring for dissolving to obtain water phase; 3) adding the oil phase into the water phase, reacting and curing, and filtering; 4) washing the filtered beads with hot water, and then washing with ethanol to obtain the macroporous adsorption resin. The invention has the following problems: toluene and xylene with certain toxicity are also used as pore-foaming agents, so that production personnel have the risk of poisoning, and the product also has certain toxicity.
Disclosure of Invention
The invention aims to provide a macroporous adsorption resin which is low in toxicity and can effectively reduce the poisoning risk of production personnel.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a macroporous adsorption resin is prepared from the following raw materials in parts by weight: 950-1050 parts of pure water, 4-6 parts of gelatin, 0.4-0.6 part of methylene blue, 90-110 parts of methyl acrylate, 9-11 parts of triallyl isocyanurate, 7-9 parts of divinylbenzene, 45-55 parts of pore-foaming agent and 1-2 parts of peroxide.
Further, the porogen of the present invention is composed of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, wherein the tetrabutylammonium-lysine is prepared by the following steps:
adding tetrabutylammonium hydroxide into water, uniformly mixing to obtain a tetrabutylammonium hydroxide aqueous solution, adding lysine into the tetrabutylammonium hydroxide aqueous solution, stirring at room temperature for reaction for 15 hours, then evaporating water at 60 ℃ in vacuum, drying at 70 ℃ in vacuum for 24 hours to obtain a crude product, adding the crude product into acetonitrile, stirring for 8 hours to obtain a mixed solution, centrifuging the mixed solution for 10 minutes to obtain a supernatant, evaporating acetonitrile at 60 ℃ in vacuum, and drying at 70 ℃ in vacuum for 24 hours to obtain tetrabutylammonium-lysine.
Further, in the tetrabutylammonium-lysine production step of the present invention, the molar ratio of tetrabutylammonium hydroxide to lysine is 1:1.5, and the centrifugation speed is 8000 rpm.
Further, the peroxide is benzoyl peroxide.
The invention also provides a preparation method of the macroporous adsorption resin.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of macroporous adsorption resin comprises the following steps:
s1, heating pure water to 50-55 ℃, adding gelatin, stirring for 20-40 minutes to dissolve the gelatin, adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and peroxide, stirring for 10-20 minutes, adding a pore-foaming agent, and continuously stirring for 10-20 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 68-70 ℃, preserving heat for 4 hours, heating to 80-82 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing for 3 times, discharging and screening;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution, heating to 90 ℃, preserving heat for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to neutrality, filtering, discharging, and packaging.
Further, in step S3 of the present invention, the temperature of the hot water is 50 ℃.
Further, in step S4 of the present invention, a 40-mesh sieve is used for the sieving.
Further, in step S5 of the present invention, the mass concentration of the sodium hydroxide solution is 20%.
Compared with the prior art, the invention has the following beneficial effects:
1) the pore-foaming agent used by the invention is composed of cyclohexane and tetrabutylammonium-lysine with low toxicity, can effectively reduce the toxicity of products and the poisoning risk of production personnel, and can be distilled out for repeated recycling, thereby reducing the environmental pollution and the cost.
2) Although the toxicity of cyclohexane is lower than that of the existing pore-forming agents such as toluene, xylene and gasoline, the pore-forming effect is poor, so that tetrabutylammonium-lysine prepared by reacting tetrabutylammonium hydroxide with lysine is used in the invention, the pore-forming effect of the pore-forming agent can be effectively improved, the adsorption performance of the macroporous adsorption resin is further improved, and the heat resistance of the macroporous adsorption resin can be further improved by the tetrabutylammonium-lysine.
3) The triallyl isocyanurate used in the invention can increase the strength of the macroporous adsorption resin, thereby prolonging the service life of the macroporous adsorption resin.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, and the exemplary embodiments and descriptions thereof herein are provided to explain the present invention but not to limit the present invention.
Example 1
The macroporous adsorption resin is prepared from the following raw materials in parts by weight: 1000 parts of pure water, 5 parts of gelatin, 0.5 part of methylene blue, 100 parts of methyl acrylate, 10 parts of triallyl isocyanurate, 8 parts of divinylbenzene, 50 parts of pore-foaming agent and 1.5 parts of benzoyl peroxide. Wherein the pore-forming agent consists of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, and the tetrabutylammonium-lysine is prepared by the following steps:
adding tetrabutylammonium hydroxide into water, uniformly mixing to obtain a tetrabutylammonium hydroxide aqueous solution, adding lysine into the tetrabutylammonium hydroxide aqueous solution, wherein the molar ratio of tetrabutylammonium hydroxide to lysine is 1:1.5, stirring and reacting for 15 hours at room temperature, then evaporating water under vacuum at 60 ℃, drying under vacuum at 70 ℃ for 24 hours to obtain a crude product, adding the crude product into acetonitrile, stirring for 8 hours to obtain a mixed solution, centrifuging the mixed solution at 8000rpm for 10 minutes to obtain a supernatant, evaporating acetonitrile under vacuum at 60 ℃, and drying under vacuum at 70 ℃ for 24 hours to obtain tetrabutylammonium-lysine.
The preparation method of the macroporous adsorption resin comprises the following steps:
s1, heating pure water to 54 ℃, adding gelatin, stirring for 30 minutes to dissolve the gelatin, then adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and benzoyl peroxide, stirring for 15 minutes, adding a pore-foaming agent, and continuously stirring for 15 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 69 ℃, preserving heat for 4 hours, heating to 81 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water at 50 ℃ for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing with water for 3 times, discharging, and screening with a 40-mesh sieve;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution with the mass concentration of 20%, heating to 90 ℃, preserving the temperature for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to be neutral, filtering, discharging, and packaging.
Example 2
The macroporous adsorption resin is prepared from the following raw materials in parts by weight: 950 parts of pure water, 6 parts of gelatin, 0.6 part of methylene blue, 90 parts of methyl acrylate, 10.5 parts of triallyl isocyanurate, 7.5 parts of divinylbenzene, 45 parts of pore-forming agent and 1 part of benzoyl peroxide. Wherein the porogen was composed of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, and the preparation procedure of tetrabutylammonium-lysine was the same as that of example 1.
The preparation method of the macroporous adsorption resin comprises the following steps:
s1, heating pure water to 50 ℃, adding gelatin, stirring for 40 minutes to dissolve the gelatin, then adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and benzoyl peroxide, stirring for 16 minutes, adding a pore-foaming agent, and continuously stirring for 14 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 70 ℃, preserving heat for 4 hours, then heating to 82 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water at 50 ℃ for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing with water for 3 times, discharging, and screening with a 40-mesh sieve;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution with the mass concentration of 20%, heating to 90 ℃, preserving the temperature for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to be neutral, filtering, discharging, and packaging.
Example 3
The macroporous adsorption resin is prepared from the following raw materials in parts by weight: 1050 parts of pure water, 4 parts of gelatin, 0.5 part of methylene blue, 95 parts of methyl acrylate, 11 parts of triallyl isocyanurate, 7 parts of divinylbenzene, 48 parts of a pore-forming agent and 2 parts of benzoyl peroxide. Wherein the porogen was composed of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, and the preparation procedure of tetrabutylammonium-lysine was the same as that of example 1.
The preparation method of the macroporous adsorption resin comprises the following steps:
s1, heating pure water to 55 ℃, adding gelatin, stirring for 20 minutes to dissolve the gelatin, then adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and benzoyl peroxide, stirring for 10 minutes, adding a pore-foaming agent, and continuously stirring for 20 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 69 ℃, preserving heat for 4 hours, heating to 81 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water at 50 ℃ for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing with water for 3 times, discharging, and screening with a 40-mesh sieve;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution with the mass concentration of 20%, heating to 90 ℃, preserving the temperature for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to be neutral, filtering, discharging, and packaging.
Example 4
The macroporous adsorption resin is prepared from the following raw materials in parts by weight: 1020 parts of pure water, 4.5 parts of gelatin, 0.4 part of methylene blue, 110 parts of methyl acrylate, 9 parts of triallyl isocyanurate, 9 parts of divinylbenzene, 55 parts of pore-forming agent and 1.1 part of benzoyl peroxide. Wherein the porogen was composed of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, and the preparation procedure of tetrabutylammonium-lysine was the same as that of example 1.
The preparation method of the macroporous adsorption resin comprises the following steps:
s1, heating pure water to 52 ℃, adding gelatin, stirring for 35 minutes to dissolve the gelatin, adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and benzoyl peroxide, stirring for 20 minutes, adding a pore-foaming agent, and continuously stirring for 10 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 68 ℃, preserving heat for 4 hours, heating to 80 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water at 50 ℃ for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing with water for 3 times, discharging, and screening with a 40-mesh sieve;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution with the mass concentration of 20%, heating to 90 ℃, preserving the temperature for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to be neutral, filtering, discharging, and packaging.
Reference example 1:
the difference from example 1 is that: the triallyl isocyanurate in the feed was replaced with methyl methacrylate.
Reference example 2:
the difference from example 1 is that: the porogen in the raw material is replaced by cyclohexane, and the preparation step of tetrabutylammonium-lysine is omitted.
Reference example 3:
the difference from example 1 is that: the porogen in the raw material is replaced by toluene, and the preparation step of tetrabutylammonium-lysine is omitted.
Comparative example: example 1 of chinese patent application No. CN 201410598735.9.
Test example 1: adsorption Performance test
The test method comprises the following steps: 0.25g of the macroporous adsorption resins of examples 1 to 4, reference examples 1 to 3 and comparative example were weighed and added to a conical flask, 50mL of 40mg/L phenol aqueous solution was added, and the mixture was subjected to ultrasonic oscillation for 2 hours, and the phenol aqueous solution after adsorption was measured for the concentration of phenol by an ultraviolet spectrophotometer to calculate the static adsorption rate of the macroporous adsorption resin to the phenol aqueous solution, and the higher the static adsorption rate, the better the adsorption performance.
The test results are shown in table 1:
| static adsorption Rate (%) | |
| Example 1 | 74.34 |
| Example 2 | 72.68 |
| Example 3 | 73.85 |
| Example 4 | 73.29 |
| Reference example 1 | 74.33 |
| Reference example 2 | 67.57 |
| Reference example 3 | 72.76 |
| Comparative example | 66.62 |
TABLE 1
As can be seen from Table 1, the static adsorption rates of examples 1 to 4 of the present invention are all higher than those of the comparative examples, indicating that the macroporous adsorbent resin of the present invention has good adsorption performance. The difference between part of the raw materials of reference examples 1-3 and example 1 shows that the static adsorption rate of reference example 2 is reduced, which indicates that tetrabutylammonium-lysine prepared by the invention can effectively improve the adsorption performance of macroporous adsorption resin.
Test example 2: toxicity testing
The test method comprises the following steps: the toxicity hazard grades of examples 1 to 4, reference examples 1 to 3 and comparative examples were determined according to the GB5044-85 standard, respectively, and a higher toxicity hazard grade indicates lower toxicity. The test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the toxicity hazard grades of examples 1-4 of the present invention are all higher than those of the comparative examples, indicating that the macroporous adsorbent resin of the present invention has low toxicity. The difference between part of the raw materials of reference examples 1-3 and example 1 indicates that the toxicity hazard level of reference example 3 is reduced to III, which indicates that the porogenic agent used in the present invention can effectively reduce the toxicity of the macroporous adsorbent resin.
Test example 3: strength test
The test method comprises the following steps: respectively carrying out air drying on the examples 1-4 and the reference examples 1-3 and the comparative examples, screening macroporous adsorption resin balls clamped on sieve pores by using a sieve with the pore diameter of 0.8mm, wetting the macroporous adsorption resin balls by using drinking water, measuring the crushing strength of 20 wetted macroporous adsorption resin balls by using a DL5 intelligent particle strength tester, and calculating the average value to obtain the crushing strength of the macroporous adsorption resin. The test results are shown in table 3:
| crush strength (N/grain) | |
| Example 1 | 9.2 |
| Example 2 | 8.8 |
| Example 3 | 9.0 |
| Example 4 | 8.7 |
| Reference example 1 | 7.6 |
| Reference example 2 | 9.1 |
| Reference example 3 | 9.2 |
| Comparative example | 7.9 |
TABLE 3
As can be seen from Table 3, the crushing strength of the inventive examples 1-4 is greater than that of the comparative examples, indicating that the macroporous adsorbent resin of the present invention has better strength. The difference between part of the raw materials of reference examples 1-3 and example 1 shows that the crushing strength of reference example 1 is significantly reduced, which indicates that the triallyl isocyanurate used in the present invention is effective for increasing the strength of the macroporous adsorbent resin.
Test example 4: heat resistance test
The test method comprises the following steps: the initial decomposition temperatures of examples 1 to 4, reference examples 1 to 2 and comparative example were measured by a thermogravimetric analyzer at a temperature rise rate of 20 ℃ per minute from room temperature to 600 ℃. The higher the initial decomposition temperature, the better the heat resistance, and the test results are shown in table 4:
| initial decomposition temperature (. degree. C.) | |
| Example 1 | 378.6 |
| Example 2 | 378.3 |
| Example 3 | 378.0 |
| Example 4 | 378.2 |
| Reference example 1 | 378.5 |
| Reference example 2 | 359.5 |
| Comparative example | 360.4 |
TABLE 4
As can be seen from Table 4, the initial decomposition temperatures of examples 1 to 4 of the present invention are all higher than those of the comparative examples, indicating that the macroporous adsorbent resin of the present invention has better heat resistance. The difference between part of the raw materials of reference examples 1-2 and example 1 and the initial decomposition temperature of reference example 2 is lowered, which shows that tetrabutylammonium-lysine prepared by the present invention can effectively improve the heat resistance of macroporous adsorbent resin.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A macroporous adsorbent resin is characterized in that: the feed is prepared from the following raw materials in parts by weight: 950-1050 parts of pure water, 4-6 parts of gelatin, 0.4-0.6 part of methylene blue, 90-110 parts of methyl acrylate, 9-11 parts of triallyl isocyanurate, 7-9 parts of divinylbenzene, 45-55 parts of pore-foaming agent and 1-2 parts of peroxide; the porogen consists of cyclohexane and tetrabutylammonium-lysine in a weight ratio of 4:1, and the tetrabutylammonium-lysine is prepared by the following steps:
adding tetrabutylammonium hydroxide into water, uniformly mixing to obtain a tetrabutylammonium hydroxide aqueous solution, adding lysine into the tetrabutylammonium hydroxide aqueous solution, stirring at room temperature for reaction for 15 hours, then evaporating water at 60 ℃ in vacuum, drying at 70 ℃ in vacuum for 24 hours to obtain a crude product, adding the crude product into acetonitrile, stirring for 8 hours to obtain a mixed solution, centrifuging the mixed solution for 10 minutes to obtain a supernatant, evaporating acetonitrile at 60 ℃ in vacuum, and drying at 70 ℃ in vacuum for 24 hours to obtain tetrabutylammonium-lysine.
2. The macroporous adsorbent resin as claimed in claim 1, wherein: in the preparation step of the tetrabutylammonium-lysine, the molar ratio of the tetrabutylammonium hydroxide to the lysine is 1:1.5, and the centrifugation speed during centrifugation is 8000 rpm.
3. The macroporous adsorbent resin as claimed in claim 1, wherein: the peroxide is benzoyl peroxide.
4. The method for preparing macroporous adsorbent resin according to any one of claims 1 to 3, wherein: the method comprises the following steps:
s1, heating pure water to 50-55 ℃, adding gelatin, stirring for 20-40 minutes to dissolve the gelatin, adding methylene blue, and continuously stirring until the mixture is uniformly mixed to obtain a water phase;
s2, mixing methyl acrylate, triallyl isocyanurate, divinylbenzene and peroxide, stirring for 10-20 minutes, adding a pore-foaming agent, and continuously stirring for 10-20 minutes to obtain an oil phase;
s3, adding the oil phase obtained in the step S2 into the water phase obtained in the step S1, heating to 68-70 ℃, preserving heat for 4 hours, heating to 80-82 ℃, preserving heat for 2 hours, heating to 95 ℃, preserving heat for 4 hours, and washing with hot water for 3 times to obtain white balls;
s4, adding the white balls obtained in the step S3 into water, heating to 100 ℃, evaporating out the pore-forming agent, washing for 3 times, discharging and screening;
s5, adding the white balls screened in the step S4 into a sodium hydroxide solution, heating to 90 ℃, preserving heat for 10 hours, cooling to room temperature, filtering to remove sodium hydroxide, washing to neutrality, filtering, discharging, and packaging.
5. The method for preparing macroporous adsorbent resin as claimed in claim 4, wherein: in step S3, the temperature of the hot water is 50 ℃.
6. The method for preparing macroporous adsorbent resin as claimed in claim 4, wherein: in step S4, a 40-mesh sieve is used for sieving.
7. The method for preparing macroporous adsorbent resin as claimed in claim 4, wherein: in step S5, the mass concentration of the sodium hydroxide solution is 20%.
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| CN103694405A (en) * | 2013-12-16 | 2014-04-02 | 无锡济民可信山禾药业股份有限公司 | Preparation method of macroporous weakly acidic cation exchange resin |
| CN109694440A (en) * | 2017-10-20 | 2019-04-30 | 中蓝晨光化工研究设计院有限公司 | A kind of new macroporous Weak-acid cation exchange resin and preparation method thereof |
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| CN1320647A (en) * | 2001-01-05 | 2001-11-07 | 南京大学 | Process for preparing macroreticular weakly acidic cationic exchange resin of acrylic series |
| CN103694405A (en) * | 2013-12-16 | 2014-04-02 | 无锡济民可信山禾药业股份有限公司 | Preparation method of macroporous weakly acidic cation exchange resin |
| CN109694440A (en) * | 2017-10-20 | 2019-04-30 | 中蓝晨光化工研究设计院有限公司 | A kind of new macroporous Weak-acid cation exchange resin and preparation method thereof |
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