CN117024654A - Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin - Google Patents
Synthesis method of low-conversion-expansion-rate acrylic weak-acid cation exchange resin Download PDFInfo
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- CN117024654A CN117024654A CN202311137315.6A CN202311137315A CN117024654A CN 117024654 A CN117024654 A CN 117024654A CN 202311137315 A CN202311137315 A CN 202311137315A CN 117024654 A CN117024654 A CN 117024654A
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- 239000002253 acid Substances 0.000 title claims abstract description 31
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 27
- 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 title claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000001913 cellulose Substances 0.000 claims abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 10
- 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 abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- 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 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 230000009466 transformation Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract 1
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 description 7
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- LZWFXVJBIZIHCH-UHFFFAOYSA-N 1-Ethenylhexyl butanoate Chemical compound CCCCCC(C=C)OC(=O)CCC LZWFXVJBIZIHCH-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to the technical field of organic synthesis of resin. The synthesis method of the low-conversion-type expansion-rate acrylic weak acid cation exchange resin comprises the following steps: (1) water phase preparation: adding water and industrial salt into a reaction vessel, heating, adding cellulose, continuously stirring, and adding methylene blue to prepare a water phase; (2) oil phase preparation: adding triethylene benzene, triallyl isocyanurate, glycerol trimethacrylate, acrylonitrile, a pore-forming agent and an initiator into a container, and fully stirring and uniformly mixing; (3) polymerization: adding the oil phase into the water phase for polymerization reaction to prepare white ball resin; (4) hydrolysis: the white ball resin and sulfuric acid solution are added into a reaction vessel for hydrolysis. The obtained resin has more compact cross-linking structure and better swelling and shrinking stability, and the transformation expansion rate is lower in the same type of resin.
Description
Technical Field
The application relates to a synthetic method of resin, belonging to the technical field of organic synthesis.
Background
The weak acid acrylic cation exchange resin is in the form of milky white or pale yellow opaque spherical particles, and is insoluble in water, acid, alkali and various organic solvents. Has the advantages of high regeneration rate, low acid consumption, large exchange capacity and the like. The large Kong Gongju beads are prepared by suspension polymerization, and then the products can be obtained through hydrolysis, post-treatment and transformation. The method is used for water treatment with high salt content of raw water, softening and dealkalizing treatment of large water amount, neutralization of waste acid and waste alkali, treatment of electroplating copper and nickel-containing wastewater, and industries of pharmacy, food, sugar production and the like.
But the space of the device is not fully utilized due to the large expansion or contraction rate in different forms or different mediums. The original acrylic weak acid cation exchange resin adopts one or two of divinylbenzene, triallylisocyanurate, glycerol trimethacrylate and the like as a cross-linking agent to be copolymerized with acrylonitrile or methyl acrylate, and toluene and 200# solvent oil are used as pore-forming agents. The obtained weak acid cation exchange resin has the advantages of not very compact structure, poor swelling and shrinking stability and higher transformation expansion rate. In view of the above-mentioned drawbacks, it is one of the difficulties in the prior art how to reduce the conversion expansion rate of the resin while retaining the exchange capacity.
Disclosure of Invention
The application aims to provide a synthesis method of low-transformation-expansion-rate acrylic acid weak acid cation exchange resin, which has the advantages of more compact cross-linking structure, better expansion and contraction stability and lower transformation expansion rate in the same type of resin.
In order to achieve the above purpose, the present application provides the following technical solutions:
the synthesis method of the low-conversion-type expansion-rate acrylic weak acid cation exchange resin comprises the following steps: (1) water phase preparation: adding water and industrial salt into a reaction container, heating to 60 ℃, stirring until the industrial salt is completely dissolved, adding cellulose, continuously stirring until the cellulose is completely dissolved, adding methylene blue, stirring until the methylene blue is completely dissolved, closing stirring, and standing to eliminate bubbles generated in the stirring process; (2) oil phase preparation: adding trivinylbenzene, triallyl isocyanurate, glycerol trimethacrylate, acrylonitrile, toluene, no. 200 solvent oil, benzoyl peroxide and azodiisobutyronitrile into a container, and fully stirring and uniformly mixing; (3) polymerization: adding the oil phase into the water phase for polymerization reaction to prepare white ball resin; (4) hydrolysis: adding white ball resin into a reaction container, adding sulfuric acid solution into the reaction container for hydrolysis, and washing with water to obtain the acrylic weak acid cation exchange resin with low conversion expansion rate.
The mass volume ratio of water, cellulose, industrial salt and methylene blue in the water phase is as follows: 450-550:1.2-1.6:90-110:1-2 (g: g: mL).
The mass ratio of the trivinylbenzene, triallyl isocyanurate, glycerol trimethacrylate, acrylonitrile, toluene, 200# solvent oil, benzoyl peroxide and azo in the oil phase is 1.5-3:3.5-5.5:2.5-3.5:87.5-91.5:15-25:12-17:0.3-0.5:0.3:0.5.
The mass ratio of the oil phase to the water phase is 0.15-0.3:1.
polymerization: adding the oil phase into the water phase, standing to eliminate bubbles generated in the adding process, stirring, adjusting to the required granularity, observing and shaping, observing and heating after shaping, keeping the temperature between 68 and 72 ℃ until the heat release is finished, preserving the heat for 4 hours, heating to 75 ℃ for 2 hours, heating to 85 ℃ for 2 hours, closing the heating, cooling to below 50 ℃, washing with water, and drying to obtain the white ball resin.
Hydrolysis: adding white ball resin into a reaction vessel, adding 54% sulfuric acid solution into the reaction vessel, stirring, heating to 100 ℃, slowly heating to 120 ℃ at a speed of 5 ℃/10 min, heating to 130 ℃ at a speed of 2 ℃/10 min, observing heat release, after the heat release is finished (sampling is added into tap water, heat release is finished when the resin is immersed into water, and vice versa), preserving heat at 130 ℃ for 8 hours, closing heating, cooling to below 50 ℃, and washing with water to obtain the low-conversion-type expansion acrylic acid series weak acid cation exchange resin.
The mass ratio of the white ball resin to the sulfuric acid solution is 1:6-10.
The prepared low-conversion-expansion-ratio acrylic weak acid cation exchange resin is applied to high-salt-content water treatment, high-water-content softening dealkalization treatment, waste acid and waste alkali neutralization, copper-nickel-containing electroplating wastewater treatment, pharmacy, food and sugar production.
Advantageous effects
The resin adopts three cross-linking agents of trivinylbenzene, triallylisocyanurate and glyceryl trimethacrylate to co-polymerize with acrylonitrile, the three cross-linking agents have higher relative purity, the required cross-linking degree can be achieved by using a small amount, and the amount of acrylonitrile for generating carboxyl is relatively large. When multiple double bond substances are polymerized simultaneously, self polymerization is a certain priority, and single or two crosslinking agents can play a certain role in reducing transformation expansion rate by increasing quantity, but at the same time, the exchange capacity is reduced, the pore diameter structure is less uniform, the use of three high-content crosslinking agents is less than that of one or two crosslinking agents, the self polymerization can be relatively reduced, the use of crosslinking agents with different structures also enables the skeleton structure of the resin to be more diversified, and the relatively more uniform structure can be obtained through the adjustment of the use amount and the combination of pore-forming agents. Toluene and 200# solvent oil are used as pore-forming agents, and weak acid cation exchange resin with relatively compact cross-linking structure, relatively good swelling and shrinking stability and relatively low transformation expansion rate in the same type of resin is obtained while the same exchange capacity is achieved. The resin of the application has a total exchange capacity of 11.31mmol/g and a transformation expansion rate as low as 29%.
Detailed Description
Example 1
The synthesis method of the low-conversion-type expansion-rate acrylic weak acid cation exchange resin comprises the following steps: (1) water phase preparation: 500g of water and 100g of industrial salt are added into a three-port bottle, the temperature is raised to 60 ℃ and stirred for 30 minutes until the industrial salt is completely dissolved, 1.5g of cellulose is added, stirring is continued for 25 minutes until the cellulose is completely dissolved, 1.5ml of 0.5% methyl blue is added, stirring is stopped after 5 minutes until the methylene blue is completely dissolved, and the mixture is kept stand for 2 minutes to eliminate bubbles generated in the stirring process.
(2) Preparing an oil phase: 2g of trivinylbenzene, 5g of triallyl isocyanurate, 3g of glycerol trimethacrylate, 90g of acrylonitrile, 20g of toluene, 15g of 200# solvent oil, 0.4g of benzoyl peroxide and 0.4g of azobisisobutyronitrile are added into a container, and the materials are fully stirred and uniformly mixed.
(3) Polymerization: adding the oil phase into the water phase, standing for 5 minutes to eliminate bubbles generated in the adding process, stirring, adjusting to the required granularity, observing and shaping, observing and releasing heat after shaping, keeping the temperature between 68 and 72 ℃ until the heat release is finished, preserving the heat for 4 hours, heating to 75 ℃ for 2 hours, heating to 85 ℃ for 2 hours, closing heating, cooling to below 50 ℃, washing with water, and drying to obtain the white ball resin.
(4) Hydrolysis: 100g of white ball resin is weighed and added into a three-mouth bottle, 800g of 54% sulfuric acid solution is added into the three-mouth bottle, stirring is started, after the temperature is raised to 100 ℃, the temperature is slowly raised to 120 ℃ at the speed of 5 ℃/10 minutes, the temperature is raised to 130 ℃ at the speed of 2 ℃/10 minutes, heat release is observed, when the heat release is finished (when the sample is added into tap water and the resin is immersed into water, the heat release is finished, and vice versa), the temperature is kept for 8 hours at 130 ℃, heating is closed, the temperature is cooled to below 50 ℃, and the acrylic acid series weak acid cation exchange resin with low conversion expansion rate is obtained through water washing.
Example 2
The synthesis method of the low-conversion-type expansion-rate acrylic weak acid cation exchange resin comprises the following steps: (1) water phase preparation: 450g of water and 110g of industrial salt are added into a three-mouth bottle, the temperature is raised to 60 ℃ and stirred for 30 minutes until the industrial salt is completely dissolved, 1.6g of cellulose is added, stirring is continued for 25 minutes until the cellulose is completely dissolved, 1mL of 0.5% methyl blue is added, stirring is stopped after 5 minutes until the methylene blue is completely dissolved, and the mixture is left stand for 2 minutes to eliminate bubbles generated in the stirring process.
(2) Preparing an oil phase: 2g of trivinylbenzene, 3.5g of triallyl isocyanurate, 3.5g of glycerol dimethacrylate, 91g of acrylonitrile, 15g of toluene, 17g of No. 200 solvent oil, 0.3g of benzoyl peroxide and 0.5g of azobisisobutyronitrile are added into a container, and the mixture is fully stirred and uniformly mixed.
(3) Polymerization: adding the oil phase into the water phase, standing for 5 minutes to eliminate bubbles generated in the adding process, stirring, adjusting to the required granularity, observing and shaping, observing and releasing heat after shaping, keeping the temperature between 68 and 72 ℃ until the heat release is finished, preserving the heat for 4 hours, heating to 75 ℃ for 2 hours, heating to 85 ℃ for 2 hours, closing heating, cooling to below 50 ℃, washing with water, and drying to obtain the white ball resin.
(4) Hydrolysis: 100g of white ball resin is weighed and added into a three-mouth bottle, 600g of 54% sulfuric acid solution is added into the three-mouth bottle, stirring is started, after the temperature is raised to 100 ℃, the temperature is slowly raised to 120 ℃ at the speed of 5 ℃/10 minutes, the temperature is raised to 130 ℃ at the speed of 2 ℃/10 minutes, heat release is observed, when the heat release is finished (when a sample is added into tap water and the resin is immersed into water, the heat release is finished, and vice versa), the temperature is kept for 8 hours at 130 ℃, heating is closed, the temperature is cooled to below 50 ℃, and the acrylic acid series weak acid cation exchange resin with low conversion expansion rate is obtained through water washing.
Example 3
The synthesis method of the low-conversion-type expansion-rate acrylic weak acid cation exchange resin comprises the following steps: (1) water phase preparation: 550g of water and 90g of industrial salt are added into a three-port bottle, the temperature is raised to 60 ℃ and stirring is carried out for 30 minutes until the industrial salt is completely dissolved, 1.2g of cellulose is added, stirring is continued for 25 minutes until the cellulose is completely dissolved, then 2mL of 0.5% methyl blue is added, stirring is stopped after 5 minutes until the methyl blue is completely dissolved, and standing is carried out for 2 minutes to eliminate bubbles generated in the stirring process.
(2) Preparing an oil phase: 1.5g of trivinylbenzene, 5.5g of triallyl isocyanurate, 2.5g of glycerol trimethacrylate, 90.5g of acrylonitrile, 25g of toluene, 12g of 200# solvent oil, 0.5g of benzoyl peroxide and 0.3g of azobisisobutyronitrile are added into a container, and the mixture is fully stirred and uniformly mixed.
(3) Polymerization: adding the oil phase into the water phase, standing for 5 minutes to eliminate bubbles generated in the adding process, stirring, adjusting to the required granularity, observing and shaping, observing and releasing heat after shaping, keeping the temperature between 68 and 72 ℃ until the heat release is finished, preserving the heat for 4 hours, heating to 75 ℃ for 2 hours, heating to 85 ℃ for 2 hours, closing heating, cooling to below 50 ℃, washing with water, and drying to obtain the white ball resin.
(4) Hydrolysis: 100g of white ball resin is weighed and added into a three-mouth bottle, 1000g of 54% sulfuric acid solution is added into the three-mouth bottle, stirring is started, after the temperature is raised to 100 ℃, the temperature is slowly raised to 120 ℃ at the speed of 5 ℃/10 minutes, the temperature is raised to 130 ℃ at the speed of 2 ℃/10 minutes, heat release is observed, when the heat release is finished (when a sample is added into tap water and the resin is immersed into water, the heat release is finished, and vice versa), the temperature is kept for 8 hours at 130 ℃, heating is closed, the temperature is cooled to below 50 ℃, and the acrylic acid series weak acid cation exchange resin with low conversion expansion rate is obtained through water washing.
The resins prepared in examples 1-3 of the present application gave the following results compared to other acrylic cation exchange resins:
110. d151, D152, D113 are all commercially available conventional products.
Claims (7)
1. A method for synthesizing low-conversion expansion acrylic weak acid cation exchange resin is characterized in that: the method comprises the following steps: (1) water phase preparation: adding water and industrial salt into a reaction container, heating to 60 ℃, stirring until the industrial salt is completely dissolved, adding cellulose, continuously stirring until the cellulose is completely dissolved, adding methylene blue, stirring until the methylene blue is completely dissolved, closing stirring, and standing to eliminate bubbles generated in the stirring process; (2) oil phase preparation: adding trivinylbenzene, triallyl isocyanurate, glycerol trimethacrylate, acrylonitrile, toluene, no. 200 solvent oil, benzoyl peroxide and azodiisobutyronitrile into a container, and fully stirring and uniformly mixing; (3) polymerization: adding the oil phase into the water phase for polymerization reaction to prepare white ball resin; (4) hydrolysis: adding white ball resin into a reaction container, adding sulfuric acid solution into the reaction container for hydrolysis, and washing with water to obtain the acrylic weak acid cation exchange resin with low conversion expansion rate.
2. The method for synthesizing an acrylic weak acid cation exchange resin according to claim 1, wherein: the mass volume ratio of water, cellulose, industrial salt and methylene blue in the water phase is as follows: 450-550:1.2-1.6:90-110:1-2 (g: g: mL).
3. The method for synthesizing an acrylic weak acid cation exchange resin according to claim 1, wherein: the mass ratio of the trivinylbenzene, triallyl isocyanurate, glycerol trimethacrylate, acrylonitrile, toluene, 200# solvent oil, benzoyl peroxide and azo in the oil phase is 1.5-3:3.5-5.5:2.5-3.5:87.5-91.5:15-25:12-17:0.3-0.5:0.3:0.5.
4. A method for synthesizing an acrylic weak acid cation exchange resin according to any one of claims 1 to 3, wherein: polymerization: adding the oil phase into the water phase, standing to eliminate bubbles generated in the adding process, stirring, adjusting to the required granularity, observing and shaping, observing and releasing heat after shaping, keeping the temperature at 68-72 ℃ until the heat release is finished, preserving heat for 4 hours, heating to 75 ℃ for 2 hours, heating to 85 ℃ for 2 hours, closing heating, cooling to below 50 ℃, washing with water, and drying to obtain the white ball resin.
5. The method for synthesizing an acrylic weak acid cation exchange resin according to claim 4, wherein: hydrolysis: adding the white ball resin into a reaction vessel, adding 54% sulfuric acid solution into the reaction vessel, stirring, heating to 100 ℃, slowly heating to 120 ℃ at a speed of 5 ℃/10 minutes, heating to 130 ℃ at a speed of 2 ℃/10 minutes, observing heat release, keeping the temperature at 130 ℃ for 8 hours after the heat release is finished, closing heating, cooling to below 50 ℃, and washing with water to obtain the low-conversion-expansion-ratio acrylic acid weak acid cation exchange resin.
6. The method for synthesizing an acrylic weak acid cation exchange resin according to claim 5, wherein: the mass ratio of the white ball resin to the sulfuric acid solution is 1:6-10.
7. Use of the resin prepared according to claim 5 or 6 in high salt content water treatment, high water softening dealkalization treatment, spent acid and spent alkali neutralization, copper and nickel electroplating wastewater treatment, pharmaceutical, food and sugar production.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082945A (en) * | 1993-05-27 | 1994-03-02 | 南开大学高分子化学研究所 | Weak-acid cation-exchange resin |
| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN115888852A (en) * | 2023-01-06 | 2023-04-04 | 山东德川化工科技有限责任公司 | Preparation process of acrylate weak acid cation exchange resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082945A (en) * | 1993-05-27 | 1994-03-02 | 南开大学高分子化学研究所 | Weak-acid cation-exchange resin |
| CN105884967A (en) * | 2015-08-26 | 2016-08-24 | 同济大学 | Contamination-resistant large-capacity macroporous weak-acid resin synthesis method |
| CN115888852A (en) * | 2023-01-06 | 2023-04-04 | 山东德川化工科技有限责任公司 | Preparation process of acrylate weak acid cation exchange resin |
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