WO2019205531A1 - 一种复合功能树脂及制备方法和应用 - Google Patents
一种复合功能树脂及制备方法和应用 Download PDFInfo
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- WO2019205531A1 WO2019205531A1 PCT/CN2018/111597 CN2018111597W WO2019205531A1 WO 2019205531 A1 WO2019205531 A1 WO 2019205531A1 CN 2018111597 W CN2018111597 W CN 2018111597W WO 2019205531 A1 WO2019205531 A1 WO 2019205531A1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OKFNSRHNCAUVOQ-UHFFFAOYSA-L calcium;decanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCCCCC([O-])=O OKFNSRHNCAUVOQ-UHFFFAOYSA-L 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000024 genotoxic Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229960002900 methylcellulose Drugs 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HDFZSPPOXSAVRI-UHFFFAOYSA-N n,n,n',n'-tetramethylethane-1,2-diamine;hydrochloride Chemical compound Cl.CN(C)CCN(C)C HDFZSPPOXSAVRI-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- 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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Definitions
- the invention belongs to the field of resins, and in particular relates to a composite functional resin, a preparation method and application thereof.
- the disinfection process is the most important way to kill pathogenic microorganisms and ensure the safety of drinking water. It mainly includes chlorine, chloramine, sodium hypochlorite, chlorine dioxide, ozone, compound disinfection and other chemical methods, as well as physical methods of ultraviolet radiation.
- chemical disinfectants react with natural organic matter, synthetic organic pollutants, bromide, iodide, etc. in the disinfection process to form various disinfection by-products such as trihalomethanes, haloacetic acids, halogenated acetonitriles and nitrosamines. Wait. Many disinfection by-products are genotoxic and carcinogenic, posing a serious threat to drinking water safety.
- UV disinfection also causes the bacteria to enter a viable but non-culturable state (S. Zhang et al. UV disinfection induces a VBNC state in Escherichia coli and Pseudomonas aeruginosa. Environ. Sci. Technol., 2015, 49: 1721-1728), Bacteria can be revived during subsequent pipeline transportation.
- there are a variety of chlorine and UV-resistant pathogens in drinking water such as Pseudomonas aeruginosa, Bacillus subtilis, etc. (T. Chiao et al. Differential resistance of drinking water bacterial populations to monochloramine disinfection, Environ. Sci. Technol. 2014, 48: 4038-4047; P. Roy et al. Chlorine resistant bacteria isolated from drinking water treatment plants in West Bengal. Desalin. Water Treat., 2017, 79: 103-107). Such bacteria are difficult to be inactivated by conventional disinfection methods and pose a greater health risk.
- a water-insoluble fixed sterilizing material is prepared by polymerizing the bactericidal monomer compound or immobilizing the bactericidal functional group on the resin material.
- the advantages of the immobilized sterilizing material are high efficiency, the bactericidal group is concentrated on the surface of the carrier to form a high concentration sterilizing agent zone; the secondary pollution of the water body can be avoided, and the solid-liquid separation is easy; the sterilizing material is neither soluble in water nor insoluble in organic matter.
- the solvent avoids the problems of toxicity, irritation and poor safety during use, and can be applied to drinking water treatment; the sterilizing material can be regenerated and reused; and the diversity of the carrier makes the application range very wide.
- Resin material is an important component in many polymer disinfectants.
- the traditional antibacterial resin is mainly divided into additive antibacterial resin and structural antibacterial resin.
- the added antibacterial resin such as the resin described in patent CN1280771A, CN102933648A, CN101891865A will be disinfected.
- the bactericide is impregnated and fixed in the resin, but there is a problem that the disinfectant is easily lost and has a short service life.
- the quaternary ammonium salt structure disinfectant has the advantages of safety and high efficiency. In recent years, there have been more and more reports on the modification of quaternary ammonium salt groups for sterilization.
- the existing resin has poor anti-interference ability, removes dissolved organic matter in water, and disinfects by-product precursors, such as nitrate, sulfate, phosphate and arsenate.
- the present invention provides a problem in that the existing resin is sterilized, the anti-interference ability is poor, the dissolved organic matter in the water is removed, the byproduct precursor is disinfected, and the anions such as nitrate, sulfate, phosphate and arsenate are poor.
- the composite functional resin, the composite functional resin of the invention has the ability to efficiently remove dissolved organic substances in water, disinfect by-product precursors, anions such as nitrate, sulfate, phosphate and arsenate, and has high bactericidal ability and resistance. The advantage of strong interference ability.
- the invention also provides a preparation method of a composite functional resin, and the invention also provides a composite functional resin application in sterilization and a composite functional resin in water treatment.
- the present invention provides a composite functional resin, the basic structure of which is of formula (I) and / or formula (II),
- a X is a quaternary ammonium group
- Y is any one or more of the formula (101), the formula (102), the formula (103), and the formula (104).
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are H or a hydrocarbon group
- the m, n, k and p are the number of repeating units, and the value ranges from 500 to 3000;
- t and q have a carbon number in the range of from 1 to 30, further preferably from 1 to 20, still more preferably from 1 to 10;
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 each have a carbon number ranging from 0 to 30;
- m, n, k, and p are preferably 500 to 2,500, more preferably 500 to 2,300, still more preferably 800 to 2,300, and most preferably 800 to 2,000.
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are a hydrocarbon group
- the number of carbon atoms is preferably It is 1 to 30, more preferably 1 to 20, still more preferably 5 to 20, and most preferably 5 to 15.
- the composite functional resin has a degree of crosslinking of 1 to 35%, the composite functional resin has a particle diameter of 10 to 2000 ⁇ m, and the surface functional N of the composite functional resin accounts for 0.005 to 50.0% of the total N content of the composite functional resin. ;
- the degree of crosslinking is preferably from 1 to 30%, more preferably from 5 to 30%, still more preferably from 5 to 25%, most preferably from 5 to 20%.
- the surface N content of the composite functional resin is preferably 0.005 to 40.0%, more preferably 1 to 30.0%, still more preferably 5.0 to 25.0%, and most preferably 10.0 to 25.0%, based on the total N content of the composite functional resin.
- the composite functional resin has a degree of crosslinking of 10 to 25%, the composite functional resin has a particle diameter of 20 to 600 ⁇ m, and the composite functional resin has a strong alkali exchange amount of 0.3 to 4.0 mmol/g.
- the composite functional resin has a resin surface charge density of 10 15 to 10 24 N + /g;
- the composite functional resin has a particle diameter of 20 to 600 ⁇ m, the bactericidal activity is high, the fluid resistance is moderate, and the sedimentation property is good;
- the particle diameter is preferably 20 to 400 ⁇ m, more preferably 20 to 300 ⁇ m, still more preferably 50 to 300 ⁇ m, and most preferably 150 to 300 ⁇ m;
- the amount of strong base exchange is preferably 1.5 to 3.0 mmol/g, more preferably 1.5 to 2.8 mmol/g, and most preferably 1.5 to 2.5 mmol/g;
- the surface charge density of the resin of the composite functional resin is preferably 10 16 to 10 24 N + /g, more preferably 10 17 to 10 24 N + /g, still more preferably 10 18 to 10 24 N + /g, most preferably 10 18 to 10 23 N + /g.
- the A X is a formula (201), a formula (202), a formula (203), a formula (204), a formula (205), a formula (206), a formula (207), a formula (208), and a formula (208). 209) in combination with one or more of formula (210),
- X is any one of Cl - , Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - , CO 3 2- , R 14 , R 15 , R 16 and R 17 are each one of H or a hydrocarbyl group;
- R 14 , R 15 , R 16 and R 17 each have a carbon number ranging from 0 to 40;
- the number of carbon atoms in the main chain is preferably from 1 to 30, still more preferably from 1 to 25, and most preferably from 1 to 20.
- the present invention also provides a method for preparing a composite functional resin, which comprises first quaternizing a first resin containing an epoxy group with a first amine salt, by controlling relevant reaction conditions and a first amine salt. a type such that the first quaternization is carried out substantially on the outer surface of the first resin, followed by a second quaternization with the second amine salt, by controlling the relevant reaction conditions and the type of the second amine salt.
- the second quaternization is carried out substantially on the inner surface of the first resin, thereby obtaining the composite functional resin of the present invention, the outer surface and the inner surface of the composite functional resin are combined with different types of quaternary ammonium groups, and the quaternization of the exterior of the resin
- the bactericidal ability of the resin is improved, and the quaternization of the resin improves the anti-interference ability of the resin, thereby achieving high-efficiency bactericidal ability and resistance to anions and natural organic substances in a water environment, and also efficiently removing solubility in water.
- the invention also provides a preparation method of a composite functional resin, comprising the following steps:
- the weight ratio of the first resin to the first amine salt in the step (1) is 1: (0.5 to 10);
- the weight ratio of the first resin to the first amine salt is preferably 1: (0.5 to 10), more preferably 1: (0.5 to 8), still more preferably 1: (0.5 to 6), and most preferably 1 :(1 ⁇ 6).
- the reaction condition in the step (1) is: the reaction time is 12 to 72 h, the stirring speed is 200 to 800 rpm, and the reaction temperature is 50 to 150 ° C;
- the reaction time in the step (1) is preferably 12 to 60 h, more preferably 20 to 60 h, still more preferably 20 to 50 h, and most preferably 20 to 40 h;
- the stirring speed in the step (1) is preferably 200 to 700 rpm, more preferably 200 to 650 rpm, still more preferably 200 to 600 rpm, and most preferably 250 to 500 rpm;
- the temperature in the step (1) is preferably 50 to 140 ° C, more preferably 50 to 130 ° C, still more preferably 60 to 130 ° C, and most preferably 60 to 120 ° C.
- the weight ratio of the weight of the first quaternized resin to the second amine salt in step (2) is 1: (0.5 to 10);
- the weight ratio of the first quaternized resin to the second amine salt is preferably 1: (0.5 to 10), more preferably 1: (0.5 to 8), still more preferably 1: (0.5 to 6) Most preferably 1: (1 to 5).
- the reaction condition in the step (2) is: the reaction time is 12 to 72 h, the stirring speed is 200 to 800 rpm, and the reaction temperature is 50 to 150 ° C;
- the reaction time in the step (2) is preferably 12 to 60 h, more preferably 20 to 60 h, still more preferably 20 to 50 h, and most preferably 20 to 40 h;
- the stirring speed in the step (2) is preferably 200 to 700 rpm, more preferably 200 to 650 rpm, still more preferably 200 to 600 rpm, and most preferably 250 to 500 rpm;
- the temperature in the step (2) is preferably 50 to 140 ° C, more preferably 50 to 130 ° C, still more preferably 60 to 130 ° C, and most preferably 60 to 120 ° C.
- the first amine salt is a formula (201), a formula (202), a formula (203), a formula (204), a formula (205), a formula (206), a formula (207), a formula (208), a combination of one or more of formula (209) and formula (210),
- X is any one of Cl - , Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - , CO 3 2-
- R 14 , R 15 , R 16 and R 17 are each one of H or a hydrocarbon group, and R 14 , R 15 , R 16 and R 17 each have a carbon number ranging from 0 to 40.
- the range of the number of carbon atoms of R 14 , R 15 , R 16 and R 17 is more preferably 6 to 30, and the range of the number of carbon atoms of R 14 , R 15 , R 16 and R 17 is still more preferably 6 to 20, R 14 , R 15 , R 16 and R 17 have a carbon number range of most preferably 10 to 20;
- the number of main chain carbon atoms is preferably any integer from 6 to 40, and further preferably any one of the number of carbon atoms in the main chain of 6 to 30, and then More preferably, the number of main chain carbon atoms is any integer from 6 to 20, and most preferably, the number of main chain carbon atoms is from 10 to 20.
- the second amine salt is of the formula (201), the formula (202), the formula (203), the formula (204), the formula (205), the formula (206), the formula (207), the formula (208), a combination of one or more of formula (209) and formula (210),
- X is any one of Cl - , Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - , CO 3 2-
- R 14 , R 15 , R 16 and R 17 are each one of H or a hydrocarbon group, and R 14 , R 15 , R 16 and R 17 each have a carbon number ranging from 0 to 40.
- the range of the number of carbon atoms of R 14 , R 15 , R 16 and R 17 is more preferably from 0 to 30, and the range of the number of carbon atoms of R 14 , R 15 , R 16 and R 17 is still more preferably from 0 to 20, R 14 , The range of the number of carbon atoms of R 15 , R 16 and R 17 is most preferably from 0 to 15;
- the number of main chain carbon atoms is any integer from 1 to 20, more preferably from 1 to 15, and most preferably from 1 to 10.
- the solvent C is water, methanol, ethanol, acetone, acetonitrile, benzene, toluene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, ethyl acetate, petroleum ether, hexane, diethyl ether and a combination of one or more of carbon chlorides, which are water, methanol, ethanol, acetone, acetonitrile, benzene, toluene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, ethyl acetate A combination of one or more of petroleum ether, hexane, diethyl ether and carbon tetrachloride.
- step (1) the following steps are further included:
- step (c) preparing the first resin: adding the oil phase in the step (b) to the aqueous phase in the step (a), stirring, heating, controlling the temperature at 50 to 120 ° C, reacting for 2 to 10 hours, and then controlling The temperature is between 80 and 150 ° C, the reaction is carried out for 2 to 12 hours, cooled to room temperature, extracted, and washed to obtain a first resin.
- the dispersing agent in the step (a) is hydroxyethyl cellulose, gelatin, polyvinyl alcohol, activated calcium phosphate, guar gum, methyl cellulose, sodium dodecylbenzene sulfonate and lignosulfonic acid.
- step (b) a combination of one or more of sodium, the sodium salt of step (a) being a combination of one or more of trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and sodium chloride, in step (b)
- the crosslinking agent is ethylene glycol diethyl diallyl ester, ethylene glycol dimethacrylate, divinylbenzene, triallyl cyanurate and trimethylolpropane trimethacrylate.
- the porogen in the step (b) is cyclohexanol, isopropanol, n-butanol, 200# solvent oil, toluene, xylene, ethyl acetate, n-octane and iso One or a combination of octanes;
- the initiator of step (b) is a combination of one or more of azobisisobutyronitrile and benzoyl peroxide.
- the molar ratio of the first monomer to the cross-linking agent in the step (b) is 1: (0.05-0.3), and the molar ratio of the first monomer to the porogen is 1: (0.1) ⁇ 0.5), the initiator weight is from 0.5 to 1.5% by weight based on the total weight of the oil phase.
- the basic structure of the first resin is one or a combination of the formula (301), the formula (302), the formula (303), and the formula (304).
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are H or a hydrocarbon group
- the m, n, k and p are the number of repeating units, and the value ranges from 500 to 3000;
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 each have a carbon number ranging from 0 to 30;
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are a hydrocarbon group
- the number of carbon atoms is preferably It is 1 to 30, more preferably 1 to 20, still more preferably 5 to 20, and most preferably 5 to 15.
- t and q have a carbon number in the range of 1 to 30, and the carbon atoms of t and q are in the range of 1 to 30, further preferably 1 to 20, still more preferably 1 to 10;
- the first monomer is a combination of one or more of the formula (401), the formula (402), the formula (403), and the formula (404).
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are H or a hydrocarbon group;
- t and q have a carbon number in the range of 1 to 30, and the carbon atoms of t and q are in the range of 1 to 30, further preferably 1 to 20, still more preferably 1 to 10;
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 each have a carbon number ranging from 0 to 30;
- R 0 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are a hydrocarbon group
- the number of carbon atoms is preferably It is 1 to 30, more preferably 1 to 20, still more preferably 5 to 20, and most preferably 5 to 15.
- the invention also provides an application of a composite functional resin in the sterilization, wherein the composite functional resin is the composite functional resin obtained as described above.
- the present invention also provides the use of a composite functional resin in the water treatment, which is the above-mentioned composite functional resin.
- the composite functional resin of the present invention has a high removal rate of pathogenic bacteria in water, and in some cases, it can reach 99.9% or more, and the regenerated resin still has strong sterilization ability, long service life, and reduces subsequent disinfection. Load, reduce the amount of disinfectant used, and reduce operating costs;
- the composite functional resin of the invention can effectively reduce the antagonism of chlorination of quaternary ammonium salt resin with chloride ion (or equivalent anion) of less than 1000 mg/L or less than 3 mg/L of natural organic matter in a water environment, and is close to
- the bactericidal efficiency of quaternary ammonium salt resin in ionic water environment improves the anti-interference ability of anion and high concentration natural organic matter such as high concentration of chloride ion in water environment;
- the composite functional resin of the invention has good organic matter removal rate at the same time, effectively removes precursors of disinfection by-products, and various anionic pollutants such as nitrates and phosphates, and reduces subsequent disinfection processes such as chlorine gas and ozone.
- the various types of disinfection by-products produced in the process, the composite functional resin has excellent sedimentation performance, and the fluidized bed device can be used to realize large-volume treatment;
- the present invention also provides a method for preparing a composite functional resin, which comprises first quaternizing a first resin containing an epoxy group and a first amine salt, and controlling the relevant reaction conditions and the first
- the type of amine salt is such that the first quaternization is carried out substantially on the outer surface of the first resin, followed by a second quaternization with the second amine salt, by controlling the relevant reaction conditions and the second amine salt.
- the type is such that the second quaternization is carried out substantially on the inner surface of the first resin, thereby obtaining the composite functional resin of the present invention.
- Figure 1 is a sterilizing efficiency of Pseudomonas aeruginosa of a resin A0 of a preferred embodiment 1 of the present invention at different Cl - concentrations;
- 3 is a sterilization efficiency of Pseudomonas aeruginosa of a resin A0 according to a preferred embodiment 1 of the present invention at different NOM concentrations;
- Figure 4 is a graph showing the bactericidal efficiency of the composite functional resin A1 against Pseudomonas aeruginosa at different NOM concentrations according to a preferred embodiment 2 of the present invention
- Figure 5 is a first embodiment of the present invention, in a preferred embodiment 7, a preferred embodiment 10 and a preferred embodiment 14, for each of the first quaternized resins and The second quaternized resin, measured by surface nitrogen content and total nitrogen content, respectively, characterized that the first quaternization mainly occurs on the surface of the resin under the control of specific reaction conditions, and the second quaternization mainly occurs inside the resin;
- Figure 6 is an infrared spectrum (F T I R) of the present invention, wherein a C-N stretching vibration absorption peak after quaternization occurs at 1105 cm -1 , a is an infrared spectrum of the first resin of Example 1, and b is the infrared spectrum of Example 1. Infrared spectrum of resin A0, c is an infrared spectrum of composite functional resin A1 of Example 2.
- Formulating 500 g of aqueous phase weigh 2.5 g of hydroxyethyl cellulose, 25 g of sodium sulfate, and the rest is water;
- the first monomer is glycidyl methacrylate, 60g of glycidyl methacrylate (GMA), 10g of divinylbenzene (DVB), and 0.6g of azo Isobutyl ester, 1.8g benzoyl peroxide, 30g cyclohexanol, added to a three-necked flask and heated to 60 ° C, reacted for 8h, then heated to 90 ° C, reacted for 4h; cooled to room temperature, charged white or off-white acrylic acid The resin ball is extracted, dried, and dried.
- the acrylic resin is the first resin.
- the acrylic resin (average particle size 500 um) was synthesized and sorted, and 80 g of the first amine salt was weighed.
- the first amine salt was dodecyl dimethylamine hydrochloride, and 20 g of the first resin and 80 g of ten were Dialkyl dimethylamine hydrochloride was placed in a 250 mL three-necked flask, temperature controlled at 60 ° C, stirred at 200 rpm, solvent was methanol, ethanol, methanol / ethanol volume ratio of 3:7, recondensation reaction for 24 h, cooling and filtration, Extracted (using methanol, ethanol, acetone), rinsed thoroughly with deionized water to obtain the first quaternized resin, and the strong base exchange amount was determined to be 1.51 mmol/g, and the surface charge density of the resin was about 1.98*. 10 23 N + /g, the surface N content of the resin accounts for 21.8% of the total N content of the resin, and the product number of the
- the bactericidal performance of the resin A0 obtained in this example was evaluated as follows:
- Pseudomonas aeruginosa ATCC 15442 was selected. After the nutrient broth was cultured, the NOM was diluted to 10 6 CFU/mL with 0 mg/L, 1 mg/L, 3 mg/L, 5 mg/L and 10 mg/L concentrations; 100 mL was prepared. The experimental bacterial solution was transferred into a 250 mL Erlenmeyer flask, 0.5 g of resin A0 was added, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; finally, 100 ⁇ l of each was taken for plate coating counting, and the sterilization efficiency was calculated. The evaluation results are shown in Fig. 3.
- the corresponding sterilization efficiencies are 99.93%, 99.82%, 63.53%, 35.29, respectively. % and 13.52%.
- a is an infrared spectrum of the first resin of the present embodiment
- b is an infrared spectrum of the resin A0 of the present embodiment
- NOM natural organic matter, referred to as NOM
- NOM mainly refers to oils, sugars, proteins, natural rubber, and other organic substances widely distributed in nature. Since these substances are organic compounds synthesized in living organisms, they are called natural organic substances.
- Formulating 500 g of aqueous phase weigh 2.5 g of hydroxyethyl cellulose, 25 g of sodium sulfate, and the rest is water;
- the first monomer is glycidyl methacrylate, 60g of glycidyl methacrylate (GMA), 10g of divinylbenzene (DVB), and 0.6g of azo Isobutyl ester, 1.8g benzoyl peroxide, 30g cyclohexanol, added to a three-necked flask and heated to 60 ° C, reacted for 8h, then heated to 90 ° C, reacted for 4h; cooled to room temperature, charged white or off-white resin The ball is extracted, washed, and dried to obtain a first resin.
- GMA g of glycidyl methacrylate
- DVB divinylbenzene
- azo Isobutyl ester 0.6g
- benzoyl peroxide 30g cyclohexanol
- the first resin (average particle size 500 um) was synthesized and sorted, and 80 g of the first amine salt was weighed.
- the first amine salt was dodecyl dimethylamine hydrochloride, and 20 g of the first resin and 80 g were used.
- Dodecyl dimethylamine hydrochloride was placed in a 250 mL three-necked flask, temperature controlled at 60 ° C, stirred at 400 rpm, solvent methanol, ethanol, methanol / ethanol volume ratio of 3:7, recondensation reaction for 24 h, cooling to room temperature Filtration, absolute ethanol and deionized water were rinsed twice to obtain the first quaternized resin, numbered A1-1, totaling 21.05 g; the first quaternized resin was added to the washed 250 mL. The second amine salt is added to the three-necked bottle.
- the second amine salt is triethylamine hydrochloride
- 60 g of triethylamine hydrochloride is added
- the solvent is 40% ethanol
- the temperature is controlled at 70 ° C
- the mixture is stirred at 250 rpm.
- the condensation reaction was carried out for 30 h, cooled and filtered, Soxhlet extraction (methanol, ethanol, acetone), and thoroughly rinsed with deionized water to obtain the composite functional resin of the present invention, and the strong alkali exchange amount was determined to be 2.15 mmol/g, and the surface of the composite functional resin was measured.
- the charge density is about 2.08*10 23 N + /g
- the surface N content of the composite functional resin accounts for 16.1% of the total N content of the composite functional resin.
- the product number of the composite functional resin is A1, a total of 22.50g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 2700 to 3000;
- c is an infrared spectrum of the composite functional resin A1 of the present embodiment.
- the bactericidal performance of the composite functional resin A1 obtained in this example was evaluated as follows:
- the corresponding sterilization efficiency is 99.99%, 99.95%, 99.81%, 85.45, respectively. % and 50.55%.
- Pseudomonas aeruginosa ATCC 15442 was selected. After the nutrient broth was cultured, the NOM was diluted to 10 6 CFU/mL with 0 mg/L, 1 mg/L, 3 mg/L, 5 mg/L and 10 mg/L concentrations; 100 mL was prepared. The experimental bacterial solution was transferred into a 250 mL Erlenmeyer flask, 0.5 g of resin A1 was added, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; finally, 100 ⁇ l of each was taken for plate coating counting, and the sterilization efficiency was calculated. The evaluation results are shown in Fig. 4.
- the corresponding sterilization efficiencies are 99.99%, 99.94%, 99.88%, 80.60, respectively. % and 39.19%.
- the first monomer of this embodiment is selected from the formula (401).
- Formulate 500g of aqueous phase weigh 2.5g of methyl cellulose, 5g of sodium dodecylbenzene sulfonate, 50g of sodium sulfate, and the rest is water;
- the first resin (average particle size 500 um) was synthesized and sorted, and 80 g of the first amine salt was weighed.
- the first amine salt was N,N-dimethyloctylamine hydrochloride, and 20 g of the first resin was obtained.
- 120g of N,N-dimethyloctylamine hydrochloride was placed in a 250mL three-necked flask, controlled at 70 ° C, stirred at 300 rpm, the solvent was N, N dimethylformamide, and the reaction was condensed for 30 h, and cooled to room temperature.
- the first quaternized resin numbered A2-1, totaling 21.30 g; the first quaternized resin was added to the washed 250 mL.
- a second amine salt is added.
- the second amine salt is trimethylamine hydrochloride, 50 g of trimethylamine hydrochloride is added, the solvent is acetonitrile, the temperature is controlled at 70 ° C, the mixture is stirred at 300 rpm, and the reaction is condensed for 24 hours.
- the composite functional resin of the present invention was thoroughly rinsed to obtain the composite functional resin of the present invention, and the strong base exchange amount was determined to be 2.25 mmol/g, and the surface charge density of the composite functional resin was about 2.72. * 10 23 N + / g, N content of the composite function of the total surface of the resin content of the composite function N 20.0% resin, the resin complex function Product number A2, a total of 21.80g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 2500 to 2700;
- the surface nitrous content and the total nitrogen content of the first quaternized resin A2-1 were measured, and the surface nitrogen content and total nitrogen content of the composite functional resin A2 were measured, and FIG. 5 was obtained.
- the first quaternization of the present embodiment mainly occurs on the surface of the resin, and the second quaternization mainly occurs inside the resin.
- the first monomer of this embodiment is selected from the formula (401).
- the first amine salt is selected from the formula (205), when X - is Cl - , the first amine salt is the formula (205-1);
- the second amine salt is selected from the formula (201), when X - is Cl - , the second amine salt is the formula (201-1);
- Formulate 500g of aqueous phase weigh 2.5g gelatin, 2.5g guar gum, 50g sodium sulfate, 50g sodium chloride, the rest is water;
- 500 g of the aqueous phase was placed in a 2 L three-necked flask, and the stirring speed was controlled at 280 rpm.
- the first resin (particle size 10 um) was synthesized and sorted, and 20 g of the first resin and 100 g of the first amine salt were placed in a 250 mL three-necked bottle.
- the first amine salt was of the formula (205-1).
- the compound was controlled at a temperature of 85 ° C, stirred at 400 rpm, the solvent was toluene, and the reaction was refluxed for 24 hours, cooled to room temperature, filtered, and rinsed twice with anhydrous ethanol and deionized water to obtain a first quaternized resin, numbered A3-1, a total of 20.85 g; the first quaternized resin was added to a washed 250 mL three-necked flask, and 50 g of a second amine salt was added.
- the second amine salt was a compound of the formula (201-1).
- the solvent is ethane, the temperature is controlled at 60 ° C, the mixture is stirred at 480 rpm, and the condensation reaction is carried out for 40 hours.
- the mixture is cooled and filtered, Soxhlet extraction (using methanol, ethanol, acetone), and thoroughly rinsed with deionized water to obtain the composite functional resin of the present invention.
- the exchange capacity of the strong base is 0.33mmol/g
- the surface charge density of the composite functional resin is about 2.01*10 19 N + /g
- the surface N content of the composite functional resin accounts for 10.12% of the total N content of the composite functional resin.
- the product number of the composite functional resin is A3, a total of 21.50g.
- X - of the composite functional resin A3 is any one of Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - and CO 3 2- Similar effect.
- the number of repeating units of the composite functional resin in this embodiment ranges from 2000 to 2500;
- the first monomer of this embodiment is selected from the formula (403).
- R 2 is -H
- R 3 is -CH 3
- R 4 is -H
- R 5 is -H
- the first monomer structure is a formula ( 403-1)
- the first amine salt is selected from the compound represented by formula (208), and when X is I - , the first amine salt is formula (208-1)
- the second amine salt is selected from the formula (202).
- R 14 is -CH 3 and X - is Cl -
- the second amine salt is (202-2).
- Formulate 500g of aqueous phase weigh 2.5g of polyvinyl alcohol, 15g of sodium chloride, and the rest is water;
- first resin (average particle size 2000 um), 20 g of the first resin and 80 g of the compound of the formula (208-1) were placed in a 250 mL three-necked flask, controlled at 70 ° C, stirred at 250 rpm, and the solvent was Carbon tetrachloride, condensed for 10h, cooled to room temperature, filtered, rinsed with absolute ethanol and deionized water twice to obtain the first quaternized resin, numbered B1-1, a total of 20.90g; The first quaternized resin was added to a washed 250 mL three-necked flask, 80 g of the compound of the formula (202-2) was added, the solvent was ethyl acetate, the temperature was controlled at 65 ° C, the mixture was stirred at 300 rpm, and the condensation reaction was carried out for 40 hours.
- the composite functional resin of the present invention Filtration, Soxhlet extraction (methanol, ethanol, acetone can be), rinse thoroughly with deionized water to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 0.3073 mmol/g, and the surface charge density of the composite functional resin is about 9.01*10 15 N + /g, the surface N content of the composite functional resin accounts for 0.005% of the total N content of the composite functional resin, and the product number of the composite functional resin is B1, totaling 21.59 g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 1,500 to 2,000.
- the first monomer of this embodiment is composed of two different first monomers.
- the first first monomer is selected from the group consisting of formula (403), when R 2 is -CH 3 , R 3 is -CH 3 , R 4 is -H, and R 5 is -H, the first first monomer structure For the formula (403-2),
- the second first monomer is glycidyl methacrylate (GMA);
- the first amine salt in this embodiment is N,N'-dibenzylethylenediamine hydrochloride
- the second amine salt is selected from the formula (203), and when X - is Cl - , the second amine salt is the formula (203-1)
- Formulate 500g of aqueous phase weigh 2.5g of polyvinyl alcohol, 1.5g of hydroxyethyl cellulose, 25g of sodium chloride, and the rest is water;
- the first resin (average particle size 100 um) was synthesized and sorted, and 20 g of the first resin and 50 g of N,N'-dibenzylethylenediamine hydrochloride were placed in a 250 mL three-necked flask, and the temperature was controlled at 110 ° C, and the mixture was stirred at 280 rpm.
- the solvent is toluene, the reaction is condensed for 24 hours, cooled to room temperature, filtered, and rinsed twice with anhydrous ethanol and deionized water to obtain a first quaternized resin, numbered B2-1, totaling 21.51 g;
- the first quaternized resin was added to a washed 250 mL three-necked flask, 80 g of a second amine salt was added, the solvent was ethanol, the temperature was controlled at 70 ° C, the mixture was stirred at 380 rpm, and the reaction was refluxed for 30 hours, cooled and filtered, and Soxhlet extraction ( Methanol, ethanol, acetone can be washed thoroughly with deionized water to obtain the composite functional resin of the present invention, and the strong base exchange amount is 1.46 mmol/g, and the surface charge density of the composite functional resin is about 1.39*10 23 N + / g, the surface N content of the composite functional resin accounts for 15.8% of the total N content of the
- the number of repeating units of the composite functional resin in this embodiment ranges from 2000 to 2300;
- X - of the composite functional resin B2 is any one of Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - and CO 3 2- Similar effect.
- the first monomer of this embodiment is selected from the group consisting of formula (403), when R 2 is -H, R 3 is -CH 3 , R 4 is -CH 2 CH 3 , and R 5 is -H, the first monomer structure For the formula (403-3),
- the first amine salt in this embodiment is N,N-dimethyl-n-octylamine hydrochloride, and the second amine salt in this embodiment is trimethylamine hydrochloride;
- Formulating 500 g of aqueous phase weighing 2.5 g of methylcellulose, 2.5 g of hydroxyethylcellulose, 25 g of sodium sulfate, 25 g of sodium chloride, and the balance being water;
- the first resin (average particle size 500 um) was synthesized and sorted, and 20 g of the first resin and 100 g of N,N-dimethyl-n-octylamine hydrochloride were placed in a 250 mL three-necked flask, temperature-controlled at 60 ° C, and stirred at 380 rpm.
- the solvent is ethanol
- the condensation reaction is carried out for 40 hours, cooled to room temperature, filtered, and rinsed twice with anhydrous ethanol and deionized water to obtain a first quaternized resin, numbered B3-1, totaling 21.35 g;
- a quaternized resin was added to a washed 250 mL three-necked flask, 60 g of trimethylamine hydrochloride was added, the solvent was methanol, the temperature was controlled at 70 ° C, the mixture was stirred at 300 rpm, and the reaction was refluxed for 24 hours, cooled and filtered, and Soxhlet extraction ( Methanol, ethanol, acetone can be washed thoroughly with deionized water to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 2.12 mmol/g, and the surface charge density of the composite functional resin is about 2.44*10 23 N + / g, the surface N content of the composite functional resin accounts for 19.1% of the total
- the number of repeating units of the composite functional resin in this embodiment ranges from 500 to 1000;
- the surface nitrogen content and total nitrogen content of the first quaternized resin B3-1 were measured, and the surface nitrogen content and the total nitrogen content of the composite functional resin B3 were measured, and FIG. 5 was obtained.
- the first quaternization of the present embodiment mainly occurs on the surface of the resin, and the second quaternization mainly occurs inside the resin.
- the first monomer of this embodiment is composed of two different first monomers.
- the first first monomer is selected from the group consisting of formula (403).
- R 2 is -H
- R 3 is -CH 3
- R 4 is -H
- R 5 is -H
- the first first monomer structure is Formula (403-1)
- the second first monomer is glycidyl methacrylate (GMA);
- the first amine salt is dioctadecylmethylamine hydrochloride, and in this embodiment the second amine salt is trimethylamine hydrochloride;
- Formulate 500g of water phase weigh 1.25g Gug, 1.25g sodium lignosulfonate, 25g sodium sulfate, 15g sodium bicarbonate, the rest is water;
- the first resin (average particle size 10 um) was synthesized and sorted, and 20 g of the first resin and 100 g of tetramethylethylenediamine hydrochloride were placed in a 250 mL three-necked flask, temperature-controlled at 120 ° C, stirred at 340 rpm, and the solvent was N.
- N-dimethylformamide condensed for 40h, cooled to room temperature, filtered, rinsed with anhydrous ethanol and deionized water twice to obtain the first quaternized resin, numbered B4-1, totaling 21.20g;
- the first quaternized resin was added to a washed 250 mL three-necked flask, 80 g of trimethylamine hydrochloride was added, the solvent was carbon tetrachloride, the temperature was controlled at 70 ° C, the mixture was stirred at 300 rpm, and the condensation reaction was carried out for 40 hours.
- Soxhlet extraction (methanol, ethanol, acetone), fully rinsed with deionized water to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 3.99 mmol/g, and the surface charge density of the composite functional resin is about 1.20. *10 24 N + /g, the surface N content of the composite functional resin accounts for 49.87% of the total N content of the composite functional resin, and the product number of the composite functional resin is B4, which is 22.75 g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 1200 to 1800.
- the first amine salt is cetyldimethylamine salt
- the second amine salt is tripropylamine hydrochloride
- Formulate 500g of water phase weigh 2.5g of polyvinyl alcohol, 5g of ammonium bicarbonate, and the rest is water;
- the first resin (average particle size 100 um) was synthesized and sorted, 20 g of the first resin and 80 g of cetyldimethylamine salt were placed in a 250 mL three-necked flask, temperature-controlled at 100 ° C, stirred at 280 rpm, and the solvent was toluene.
- the condensed reaction was carried out for 30 hours, cooled to room temperature, filtered, and rinsed twice with anhydrous ethanol and deionized water to obtain a first quaternized resin, numbered C1-1, totaling 21.80 g;
- the resin was added to a washed 250 mL three-necked flask, 80 g of tripropylamine hydrochloride was added, the solvent was carbon tetrachloride, the temperature was controlled at 70 ° C, the mixture was stirred at 300 rpm, and the condensation reaction was carried out for 40 hours.
- the mixture was cooled and filtered, and Soxhlet extraction (methanol).
- the composite functional resin of the present invention is fully rinsed to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 1.90 mmol/g, and the surface charge density of the composite functional resin is about 2.16*10 23 N + /g
- the surface N content of the composite functional resin accounts for 18.9% of the total N content of the composite functional resin, and the product number of the composite functional resin is C1, which is 22.55 g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 1,000 to 1600.
- the first monomer of this embodiment is composed of two different first monomers.
- the second first monomer is glycidyl methacrylate (GMA);
- the first amine salt is N,N-dimethylhexylamine hydrochloride
- the second amine salt is trimethylamine hydrochloride
- Formulating 500 g of aqueous phase weighing 1.5 g of polyvinyl alcohol, 1.5 g of hydroxyethyl cellulose, 5 g of ammonium hydrogencarbonate, and the balance being water;
- the first resin (average particle size 500um), place 20g of the first resin and 40g of N,N-dimethylhexylamine hydrochloride in a 250mL three-necked flask, control the temperature at 70 ° C, stir 450rpm, solvent For ethanol, condensed for 20h, cooled to room temperature, filtered, rinsed with anhydrous ethanol and deionized water twice to obtain the first quaternized resin, numbered C2-1, totaling 21.89g; The second quaternized resin was added to a washed 250 mL three-necked flask, 70 g of trimethylamine hydrochloride was added, the solvent was methanol, the temperature was controlled at 70 ° C, the mixture was stirred at 300 rpm, and the reaction was refluxed for 24 hours, cooled and filtered, and Soxhlet extraction (methanol).
- the composite functional resin of the present invention is fully rinsed to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 2.35 mmol/g, and the surface charge density of the composite functional resin is about 3.04*10 23 N + /g
- the surface N content of the composite functional resin accounts for 21.5% of the total N content of the composite functional resin, and the product number of the composite functional resin is C2, which is 23.05 g.
- the surface nitrogen content and the total nitrogen content of the first quaternized resin C2-1 were measured, and the surface nitrogen content and total nitrogen content of the composite functional resin C2 were measured, and FIG. 5 was obtained.
- the first quaternization of the present embodiment mainly occurs on the surface of the resin, and the second quaternization mainly occurs inside the resin.
- the first monomer of this embodiment is composed of two different first monomers.
- the second first monomer is glycidyl methacrylate (GMA);
- the first amine salt is selected from the formula (206).
- R 14 is -H, and X is Cl -
- the first amine salt is the formula (206-1).
- the second amine salt is selected from the formula (202), when R 14 is -H, when X is Cl - , the second amine salt is of the formula (202-1)
- Formulate 500g of aqueous phase weigh 2.5g guar gum, 5g sodium dodecylbenzene sulfonate, 5g ammonium bicarbonate, and the rest is water;
- the first resin (average particle size 200 um) was synthesized and sorted, 20 g of the first resin and 100 g of the first amine salt were placed in a 250 mL three-necked flask, temperature-controlled at 120 ° C, stirred at 350 rpm, and the solvent was N, N-dimethyl Amide, condensed reaction for 30h, cooled to room temperature, filtered, rinsed with absolute ethanol and deionized water twice to obtain the first quaternized resin, numbered C3-1, totaling 21.15g;
- the quaternized resin was added to a washed 250 mL three-necked flask, 40 g of a second amine salt was added, the solvent was ethyl acetate, the temperature was controlled at 70 ° C, stirred at 300 rpm, and the reaction was refluxed for 40 h, cooled and filtered, and Soxhlet extraction (methanol) One or a combination of ethanol and acetone can be thoroughly rinsed
- X - of the first amine salt and the second amine salt is any one of Br - , I - , I3 - , I5 - , I7 - , OH - , SO 4 2- , HCO 3 - and CO 3 2- A similar effect can also be achieved.
- the first monomer of this embodiment is composed of two different first monomers.
- the second first monomer is glycidyl methacrylate (GMA);
- the first amine salt is selected from the formula (204), when R 14 is -H, and X is Cl - , the first amine salt is the formula (204-1)
- the second amine salt in this embodiment is triethylamine hydrochloride
- Formulate 500g of aqueous phase weigh 2.5g guar gum, 1.5g active calcium phosphate, 7.5g ammonium bicarbonate, and the rest is water;
- the first resin (average particle size 600 um) was synthesized and sorted, and 20 g of the first resin and 100 g of the compound of the formula (204-1) were placed in a 250 mL three-necked flask, temperature-controlled at 70 ° C, stirred at 250 rpm, and the solvent was toluene.
- the condensation reaction was carried out for 24 hours, cooled to room temperature, filtered, and rinsed twice with absolute ethanol and deionized water to obtain a first quaternized resin, number C4-1, totaling 20.85 g; the first quaternary ammonium was The resin was added to a washed 250 mL three-necked flask, 60 g of triethylamine hydrochloride was added, the solvent was methanol, the temperature was controlled at 70 ° C, stirred at 250 rpm, and the condensation reaction was carried out for 30 h, cooled and filtered, and Soxhlet extraction (methanol, ethanol).
- Both acetone and acetone can be rinsed thoroughly to obtain the composite functional resin of the present invention, and the strong base exchange amount is 1.87 mmol/g, and the surface charge density of the composite functional resin is about 2.13*10 23 N + /g.
- the surface N content of the functional resin accounts for 18.9% of the total N content of the composite functional resin, and the product number of the composite functional resin is C4, which is 21.60 g.
- the first monomer of this embodiment is selected from the formula (404).
- R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are H, the structural formula of the first monomer is Formula (404-1)
- the first amine salt is dodecyldimethylamine hydrochloride and the second amine salt is trimethylamine hydrochloride;
- Formulate 500g of water phase weigh 5g guar gum, 10g active calcium phosphate, 7.5g sodium chloride, and the rest is water;
- the nitrogen gas was kept at room temperature for 10 minutes, and then heated to a polymerization temperature of 50 ° C for 2 hours, and then heated to 80 ° C for 2 hours; cooled to room temperature, washed, extracted, and air-dried to obtain a first resin.
- the first resin (average particle size 20 um) was synthesized and sorted, 20 g of the first resin and 60 g of dodecyldimethylamine hydrochloride were placed in a 250 mL three-necked flask, temperature controlled at 75 ° C, stirred at 300 rpm, and the solvent was ethanol. , condensed reaction for 35h, cooled to room temperature, filtered, rinsed with anhydrous ethanol and deionized water twice to obtain the first quaternized resin, numbered D1-1, totaling 21.35g; the first season mentioned above The ammonium resin was added to a washed 250 mL three-necked flask, and 50 g of the second amine salt trimethylamine hydrochloride was added.
- the solvent was methanol, the temperature was controlled at 70 ° C, the mixture was stirred at 300 rpm, and the reaction was refluxed for 24 hours. The mixture was cooled and filtered, and Soxhlet extraction was carried out. (Methanol, ethanol, acetone), deionized water was thoroughly rinsed to obtain the composite functional resin of the present invention, and the strong alkali exchange amount was determined to be 2.08 mmol/g, and the surface charge density of the composite functional resin was about 2.42*10 23 N + /g.
- the surface N content of the composite functional resin accounts for 19.3% of the total N content of the composite functional resin, and the product number of the composite functional resin is D1, which is 22.18 g.
- the first monomer of this embodiment is selected from the formula (404).
- R 6 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are H, and R 7 is -CH 3 , the first single The structural formula of the body is (404-2)
- the first amine salt is N,N-dimethylhexylamine hydrochloride
- the second amine salt is triethylamine hydrochloride
- Formulating 500 g of aqueous phase weighing 2.5 g of hydroxyethyl cellulose, 1.5 g of methyl cellulose, 15 g of sodium sulfate, and the balance being water;
- the temperature was raised to a polymerization temperature of 85 ° C, and the reaction was carried out for 6 h, and then the temperature was raised to 115 ° C for 7 h; cooled to room temperature, washed, extracted, and air-dried to obtain a first resin.
- the first resin (average particle size 400um), place 20g of the first resin and 10g of N,N-dimethylhexylamine hydrochloride in a 250mL three-necked flask, control the temperature at 50 ° C, stir 200rpm, solvent For toluene, condensed for 12h, cooled to room temperature, filtered, rinsed with absolute ethanol and deionized water twice to obtain the first quaternized resin, numbered D2-1, totaling 21.75g; The subquaternized resin was added to a washed 250 mL three-necked flask, 10.9 g of triethylamine hydrochloride was added, the solvent was carbon tetrachloride, the temperature was controlled at 150 ° C, the mixture was stirred at 800 rpm, and the reaction was refluxed for 72 hours.
- Extracting methanol, ethanol, acetone
- deionized water is thoroughly rinsed to obtain the composite functional resin of the present invention, and the strong alkali exchange amount is determined to be 2.39 mmol/g, and the surface charge density of the composite functional resin is about 3.00*10 23 N + / g, the surface N content of the composite functional resin accounts for 20.8% of the total N content of the composite functional resin, and the product number of the composite functional resin is D2, which is 22.43 g.
- the surface nitrogen content and the total nitrogen content of the first quaternized resin D2-1 were measured, and the surface nitrogen content and the total nitrogen content of the composite functional resin D2 were measured, and FIG. 5 was obtained.
- the first quaternization of the present embodiment mainly occurs on the surface of the resin, and the second quaternization mainly occurs inside the resin.
- hydroxyethyl cellulose and methyl cellulose may also be used in gelatin, polyvinyl alcohol, activated calcium phosphate, guar gum, sodium dodecylbenzenesulfonate and sodium lignosulfonate.
- the corresponding reaction can also be achieved.
- the corresponding reaction can also be achieved by substituting sodium sulfate with a combination of one or more of trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and sodium chloride.
- ethylene glycol diethyl diallyl ester ethylene glycol dimethacrylate, triallyl cyanurate, and trimethylolpropane trimethacrylate are used for divinylbenzene.
- the combination of one or several of them can also achieve the corresponding reaction.
- cyclohexanol can also be realized by a combination of one or more of isopropanol, n-butanol, 200# solvent oil, toluene, xylene, ethyl acetate, n-octane and isooctane. The corresponding reaction.
- the first monomer of this embodiment consists of the compound represented by formula (404-2);
- the first amine salt is a compound of the formula (208-1), and the second amine salt is tripropylamine hydrochloride;
- Formulating 500 g of aqueous phase weighing 2.5 g of sodium lignosulfonate, 5 g of sodium dodecylbenzenesulfonate, 25 g of sodium sulfate, 25 g of sodium chloride, and the balance being water;
- the temperature was raised to a polymerization temperature of 120 ° C, and the reaction was carried out for 10 hours, and then the temperature was raised to 150 ° C for 12 hours; cooled to room temperature, washed, extracted, and air-dried to obtain a first resin.
- Synthesized and sorted pyridine first resin (average particle size 10 um), 20 g of the first resin and 100 g of the compound of formula (208-1) were placed in a 250 mL three-necked flask, temperature controlled at 150 ° C, stirred at 800 rpm, and the solvent was N, N-dimethylformamide, condensed for 72 h, cooled to room temperature, filtered, rinsed with absolute ethanol and deionized water twice to obtain the first quaternized resin, number D3-1, total 21.03 g; the first quaternized resin was added to a washed 250 mL three-necked flask, 105 g of tripropylamine hydrochloride was added, the solvent was methanol, the temperature was controlled at 50 ° C, the mixture was stirred at 200 rpm, and the reaction was refluxed for 12 hours, and cooled and filtered.
- Soxhlet extraction methanol, ethanol, acetone can be used
- the strong alkali exchange amount is determined to be 1.82 mmol/g
- the surface charge density of the composite functional resin is about 1.91*. 10 23 N + /g
- the surface N content of the composite functional resin accounted for 17.4% of the total N content of the composite functional resin
- the product number of the composite functional resin was D3, totaling 21.90g.
- the number of repeating units of the composite functional resin in this embodiment ranges from 500 to 800.
- the first monomer of this embodiment is a compound represented by formula (404-2);
- the first amine salt is dioctadecylmethylamine hydrochloride
- the second amine salt is a compound of the formula (202-2);
- Formulate 500g of water phase weigh 5g gelatin, 1g active calcium phosphate, 7.5g sodium chloride, and the rest is water;
- the temperature was raised to a polymerization temperature of 90 ° C, and the reaction was carried out for 10 hours, and then the temperature was raised to 120 ° C for 4 hours; cooled to room temperature, washed, extracted, and air-dried to obtain a first resin.
- the first resin (average particle size 300 um) was synthesized and sorted, 20 g of the first resin and 200 g of dioctadecylmethylamine hydrochloride were placed in a 250 mL three-necked flask, temperature-controlled at 100 ° C, stirred at 501 rpm, and the solvent was Toluene, condensed for 40 h, cooled to room temperature, filtered, rinsed with absolute ethanol and deionized water twice to obtain the first quaternized resin, numbered D4-1, totaling 21.28 g; The quaternized resin was added to a washed 250 mL three-necked flask, and 210.3 g of the compound of the formula (202-2) was added.
- the solvent was ethanol, the temperature was controlled at 100 ° C, the stirring was carried out at 497 rpm, and the condensation reaction was carried out for 40 hours.
- Extraction one or a combination of methanol, ethanol and acetone
- sufficient rinsing with deionized water to obtain the composite functional resin of the present invention and measuring the strong base exchange amount to 1.95 mmol/g, and the surface charge density of the composite functional resin is about 1.87*10 23 N + /g
- the surface N content of the composite functional resin accounts for 15.9% of the total N content of the composite functional resin
- the product number of the composite functional resin is D4, which is 22.35 g.
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- Escherichia coli ATCC 8099 was selected. After culturing the nutrient broth, the number of colonies was diluted to 10 5 CFU/mL with Cl- at 0 mg/L, 100 mg/L and 1000 mg/L. Take 100 mL of the prepared experimental bacteria solution into a 250 mL Erlenmeyer flask. The resin A0 obtained in Example 1 and Example 2 were respectively added to obtain 0.5 g of each of the resin A1, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; finally, 100 ⁇ l of each was plated and counted, and each season was calculated. Ammonium salt sterilization efficiency. The results of the assessment are summarized in the table below:
- A0 ⁇ control group (only dodecyl dimethyl tertiary amine quaternization);
- A1 ⁇ experimental group dodecyl dimethylamine hydrochloride + triethylamine hydrochloride quaternized).
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- Pseudomonas aeruginosa ATCC 15442 was selected. After the nutrient broth was cultured, the number of colonies was diluted to 10 6 CFU/mL with a concentration of 0 mg/L, 100 mg/L and 1000 mg/L. Take 100 mL of the prepared experimental liquid to 250 mL cone. In the flask, the resin A0 obtained in Example 1 and Example 2 respectively obtained 0.5 g of the resin A1, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; finally, 100 ⁇ l were respectively taken for plate coating counting, and calculation was performed. Sterilization efficiency of each quaternary ammonium salt. The results of the assessment are summarized in the table below:
- A0 - control group (only decyl dimethyl tertiary amine quaternization); A1 - experimental group (dodecyl dimethylamine hydrochloride + triethylamine hydrochloride quaternization)
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- Escherichia coli ATCC 8099 was selected, and after broth culture, the NOM (natural organic matter) of 0 mg/L, 1 mg/L, 3 mg/L and 5 mg/L was diluted to 10 5 CFU/mL colony; 100 mL of prepared experimental bacteria was taken.
- the liquid was added to a 250 mL Erlenmeyer flask, and the resin A0 obtained in Example 1 and Example 2 were respectively added to obtain 0.5 g of the resin A1, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; The coating count was used to calculate the sterilization efficiency of each quaternary ammonium salt.
- the results of the assessment are summarized in the table below:
- A0 - control group (only decyl dimethyl tertiary amine quaternization); A1 - experimental group (dodecyl dimethylamine hydrochloride + triethylamine hydrochloride quaternization)
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- Pseudomonas aeruginosa ATCC 15442 was selected. After the nutrient broth was cultured, the NOM was diluted to 10 6 CFU/mL with 0 mg/L, 1 mg/L, 3 mg/L and 5 mg/L concentrations; 100 mL of the prepared experimental liquid was taken. To a 250 mL Erlenmeyer flask, the resin A0 obtained in Example 1 and Example 2 were respectively added to obtain 0.5 g of the resin A1, and then placed in a shaker at 200 rpm, 20 ⁇ 1 ° C, 60 min; and finally 100 ⁇ l was plated separately. The cloth counts and calculates the sterilization efficiency of each quaternary ammonium salt. The results of the assessment are summarized in the table below:
- A0 - control group (only decyl dimethyl tertiary amine quaternization); A1 - experimental group (dodecyl dimethylamine hydrochloride + triethylamine hydrochloride quaternization)
- This example is a quaternary ammonium salt resin bactericidal performance and pollutant removal performance evaluation
- the experimental bacterial liquid was replaced with the actual water body.
- the water quality parameters were as follows: TOC was 2.10 mg/L, NO 3 - was 0.41 mg/L, Cl - was 68 mg/L, SO 4 2- was 55 mg/L, and the actual water body was 10 L. Adding Resin A0 and Example 2 obtained in Example 1 respectively, 50 g of Resin A1 was obtained, and then placed under stirring at 200 rpm, 20 ⁇ 1° C. for 60 min. Finally, 100 ⁇ l of each was plated and counted to calculate the quaternary ammonium salt sterilization. effectiveness. The results of the assessment are summarized in the table below:
- This example is the evaluation of the removal effect of quaternary ammonium salt resin on pathogenic bacteria and pollutants in actual drinking water.
- the water quality parameters of a tap water plant were selected.
- the water quality parameters were as follows: TOC was 3.30 mg/L, NO 3 - was 1.52 mg/L, Cl - was 48 mg/L, SO 4 2- was 27 mg/L, and the actual water body was 10 L.
- Resin A0 and Example 2 obtained in Example 1 respectively, 50 g of Resin A1 was obtained, and then placed under stirring at 200 rpm, 20 ⁇ 1° C. for 60 min. Finally, 100 ⁇ l of each was plated and counted to calculate the quaternary ammonium salt sterilization. effectiveness.
- the results of the assessment are summarized in the table below:
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- This example is a bactericidal performance evaluation of quaternary ammonium salt resin
- This example is the evaluation of the removal effect of quaternary ammonium salt resin on pathogenic bacteria and pollutants in actual drinking water.
- the water quality parameters of a tap water plant were selected.
- the water quality parameters were as follows: TOC was 2.85 mg/L, NO 3 - was 1.38 mg/L, Cl - was 65 mg/L, SO 4 2- was 34 mg/L, and the actual water body was 10 L, and then 50 g of each of the resins A2, B3, C2 and D2 synthesized in Example 3, Example 7, Example 10 and Example 14 were separately added, and then placed under stirring, 200 rpm, 20 ⁇ 1 ° C, 60 min; The plate coating count was used to calculate the sterilization efficiency of each quaternary ammonium salt.
- the results of the assessment are summarized in the table below:
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Abstract
一种复合功能树脂的基本结构为式(Ⅰ)和/或式(Ⅱ),其中,所述AX为季铵基团。针对现有树脂在杀菌的同时,抗干扰能力差,去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力差的问题,该复合功能树脂同时具备高效去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力,具备高效的杀菌能力和抗干扰能力强的优点。该复合功能树脂能在杀菌和水处理中应用。
Description
本发明属于树脂领域,具体涉及一种复合功能树脂及制备方法和应用。
消毒工艺是杀灭病原微生物,保证饮用水安全的最主要方式,主要包括氯气、氯胺、次氯酸钠、二氧化氯、臭氧、复合消毒等化学方法,以及紫外线辐射的物理方法等。但化学消毒剂在消毒过程中会与水中天然有机物、人工合成有机污染物、溴化物、碘化物等反应生成多种消毒副产物,如三卤甲烷、卤代乙酸、卤代乙腈和亚硝胺等。很多消毒副产物具有遗传毒性及致癌性,严重威胁饮用水安全。紫外消毒同时也会导致细菌进入存活但不可培养的状态(S.Zhang et al.UV disinfection induces a VBNC state in Escherichia coli and Pseudomonas aeruginosa.Environ.Sci.Technol.,2015,49:1721-1728),细菌可在后续管道运输过程中复活。此外,饮用水中存在多种氯和紫外抗性病原菌,如铜绿假单胞菌、枯草芽孢杆菌等(T.Chiao et al.Differential resistance of drinking water bacterial populations tomonochloraminedisinfection,Environ.Sci.Technol.2014,48:4038-4047;P.Roy et al.Chlorine resistant bacteria isolated from drinking water treatment plants in West Bengal.Desalin.Water Treat.,2017,79:103-107)。这类细菌难以被常规消毒方式灭活,存在较大的健康风险。
为了解决小分子杀菌剂和可溶性高分子杀菌剂的消毒副产物和余毒问题,通过将杀菌剂单体化合物聚合或将杀菌功能基团固载在树脂材料上制成水不溶性固定化杀菌材料。固定化杀菌材料的优点在于效率高,杀菌基团集中在载体表面从而形成高浓度杀菌剂区;能避免水体的二次污染,且易固液分离;杀菌材料既不溶于水,又不溶于有机溶剂,避免了在使用过程中的毒性、刺激性及使用安全性差等问题,可适用于饮用水处理;杀菌材料可再生,重复利用;同时载体的多样性使其应用范围非常广泛。树脂材料是众多高分子消毒剂中的重要组成,其中传统抗菌树脂主要分为添加型抗菌树脂和结构型抗菌树脂,添加型抗菌树脂如:专利CN1280771A、CN102933648A、CN101891865A中所描述的树脂是将消毒杀菌剂浸渍固定于树脂中,但存在消毒剂易迁移流失,使用寿命较短等问题。
季铵盐结构消毒剂具有安全高效等优点,近年来,修饰季铵盐基团的材料用来杀菌的报道越来越多。
目前的树脂用于杀菌时,存在如下问题:
(1)在杀菌的同时,容易受水环境中的有机物、重金属离子、某些阴离子表面活性剂或某些大分子阴离子化合物干扰,特别是高浓度氯离子的干扰,导致杀菌能力大大下降;
(2)在杀菌的同时,对于水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的去除能力较差。
综上,现有树脂在杀菌的同时,抗干扰能力差,去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力差。
发明内容
1、要解决的技术问题:
针对现有树脂在杀菌的同时,抗干扰能力差,去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力差的问题,本发明提供一种复合功能树脂,本发明的复合功能树脂同时具备高效去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力,具备高效的杀菌能力和抗干扰能力强的优点。本发明还提供了一种复合功能树脂的制备方法、本发明还提供了一种复合功能树脂在杀菌中的应用和一种复合功能树脂在水处理中的应用。
2、技术方案
为了解决以上问题,本发明的技术方案如下:
本发明提供了一种复合功能树脂,所述复合功能树脂的基本结构为式(Ⅰ)和/或式(Ⅱ),
其中,所述A
X为季铵基团;
Y为式(101)、式(102)、式(103)和式(104)中的任意一种或几种,
其中,所述R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为H或烃基,所述m、n、k和p为重复单元的数量,数值范围均为500~3000;
t和q的碳原子数范围为1-30,进一步优选为1-20,再进一步优选为1-10;
R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13的碳原子数范围均为0~30;
m、n、k、p优选为500~2500,进一步优选为500~2300,再进一步优选为800~2300,最优选为800~2000。
当R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为烃基时,碳原子数优选为1~30,进一步优选1~20,再进一步优选为5~20,最优选为5~15。
优选的,所述复合功能树脂的交联度为1~35%,所述复合功能树脂的为粒径10~2000μm,复合功能树脂表面N含量占所述复合功能树脂总N含量0.005~50.0%;
交联度优选为1~30%,进一步优选为5~30%,再进一步优选为5~25%,最优选为5~20%。
复合功能树脂表面N含量占所述复合功能树脂总N含量优选为0.005~40.0%,进一步优选为1~30.0%,再进一步优选为5.0~25.0%,最优选为10.0~25.0%。
优选的,所述复合功能树脂的交联度为10~25%,所述复合功能树脂的为粒径为20~600μm,所述复合功能树脂的强碱交换量为0.3~4.0mmol/g,所述复合功能树脂的树脂表面电荷密度为10
15~10
24N
+/g;
所述复合功能树脂的为粒径为20~600μm时,杀菌活性较高,且流体阻力适中,沉降性较好;
粒径优选为20~400μm,进一步优选为20~300μm,再进一步优选为50~300μm,最优选为150~300μm;
强碱交换量优选为1.5~3.0mmol/g,进一步优选为1.5~2.8mmol/g,最优选为 1.5~2.5mmol/g;
复合功能树脂的树脂表面电荷密度优选为10
16~10
24N
+/g,进一步优选为10
17~10
24N
+/g,再进一步优选为10
18~10
24N
+/g,最优选为10
18~10
23N
+/g。
优选的,所述A
X为式(201)、式(202)、式(203)、式(204)、式(205)、式(206)、式(207)、式(208)、式(209)和式(210)中的一种或几种的组合,
其中,X为Cl
-、Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-、CO
3
2-中任意一种,R
14、R
15、R
16和R
17分别为H或烃基中的一种;
R
14、R
15、R
16和R
17的碳原子数范围均为0~40;
当Ax是式(209)和式(210)时,主链碳原子数量优选为1~30,再进一步优选为1~25,最优选为1~20。
本发明还提供了一种复合功能树脂的制备方法,该方法将含有环氧基团第一树脂与第一胺盐进行第一次季铵化,通过控制相关的反应条件及第一胺盐的类型,使得第一次季铵化基本都在第一树脂的外表面进行,然后再与第二胺盐进行第二次季铵化,通过控制相关的反应条件及第二胺盐的类型,使得第二次季铵化基本都在第一树脂的内表面进行,从而得到本发明的复合功能树脂,该复合功能树脂的外表面及内表面结合了不同类型的季铵基团,树脂外部的季铵化提高了树脂的杀菌能力,树脂内部的季铵化提高了树脂的抗干扰能力,从而达到高效的杀菌能力和抗水体环境中的阴离子、天然有机物的干扰能力,同时还具备高效去除水中的溶解性有机物,消毒副产物前驱体,硝酸根、硫酸根、磷酸根和砷酸根等阴离子的能力。本发明还提供了一种复合功能树脂的制备方法,包括以下步骤:
(1)加入第一树脂、第一胺盐和溶剂C,搅拌,进行反应,进行第一次季铵化,得到第一次季铵化的树脂;
(2)加入步骤(1)所述的第一次季铵化的树脂、第二胺盐和溶剂D,搅拌,进行反应,进行第二次季铵化,得到所述复合功能树脂。
优选的,步骤(1)中所述第一树脂重量与所述第一胺盐的重量比为1:(0.5~10);
第一树脂与所述第一胺盐的重量比优选为1:(0.5~10),进一步优选为1:(0.5~8),再进一步优选为1:(0.5~6),最优选为1:(1~6)。
优选的,步骤(1)中反应条件为:反应时间为12~72h,搅拌速度为200~800rpm,反应温度为50~150℃;
步骤(1)中反应时间优选为12~60h,进一步优选为20~60h,再进一步优选为20~50h,最优选为20~40h;
步骤(1)中搅拌速度优选为200~700rpm,进一步优选为200~650rpm,再进一步优选为200~600rpm,最优选为250~500rpm;
步骤(1)中温度优选为50~140℃,进一步优选为50~130℃,再进一步优选为60~130℃,最优选为60~120℃。
优选的,步骤(2)所述第一次季铵化的树脂的重量与所述第二胺盐的重量比为1:(0.5~10);
第一次季铵化的树脂与所述第二胺盐的重量比优选为1:(0.5~10),进一步优选为1:(0.5~8),再进一步优选为1:(0.5~6),最优选为1:(1~5)。
优选的,步骤(2)中反应条件为:反应时间为12~72h,搅拌速度为200~800rpm,反应温度为50~150℃;
步骤(2)中反应时间优选为12~60h,进一步优选为20~60h,再进一步优选为20~50h,最优选为20~40h;
步骤(2)中搅拌速度优选为200~700rpm,进一步优选为200~650rpm,再进一步优选为200~600rpm,最优选为250~500rpm;
步骤(2)中温度优选为50~140℃,进一步优选为50~130℃,再进一步优选为60~130℃,最优选为60~120℃。
优选的,所述第一胺盐为式(201)、式(202)、式(203)、式(204)、式(205)、式(206)、式(207)、式(208)、式(209)和式(210)中的一种或几种的组合,
其中,X为Cl
-、Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-、CO
3
2-中任意一种,R
14、R
15、R
16和R
17分别为H或烃基中的一种,R
14、R
15、R
16和R
17的碳原子数范围均为0~40。
R
14、R
15、R
16和R
17的碳原子数范围进一步优选为6~30,R
14、R
15、R
16和R
17的碳原子数范围再进一步优选为6~20,R
14、R
15、R
16和R
17的碳原子数范围最优选为10~20;
当第一胺盐为式(209)和式(210)时,主链碳原子数量优选为6~40的任意一个整数,进一步优选为主链碳原子数量为6~30的任意一个整数,再进一步优选为,主链碳原子数量为6~20的任意一个整数,最优为,主链碳原子数量为10~20的任意一个整数。
优选的,所述第二胺盐为式(201)、式(202)、式(203)、式(204)、式(205)、式(206)、式(207)、式(208)、式(209)和式(210)中的一种或几种的组合,
其中,X为Cl
-、Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-、CO
3
2-中任意一种,R
14、R
15、R
16和R
17分别为H或烃基中的一种,R
14、R
15、R
16和R
17的碳原子数范围均为0~40。
R
14、R
15、R
16和R
17的碳原子数范围进一步优选为0~30,R
14、R
15、R
16和R
17的碳原子数范围再进一步优选为0~20,R
14、R
15、R
16和R
17的碳原子数范围最优选为0~15;
当第二胺盐为式(209)和式(210)时,主链碳原子数量为1~20的任意一个整数,再优选为1~15的任意一个整数,最优选为1~10。
优选的,所述溶剂C为水、甲醇、乙醇、丙酮、乙腈、苯、甲苯、四氢呋喃、二氯甲烷、N,N二甲基甲酰胺、乙酸乙酯、石油醚、己烷、乙醚和四氯化碳中的一种或几种的组合,所述溶剂D为水、甲醇、乙醇、丙酮、乙腈、苯、甲苯、四氢呋喃、二氯甲烷、N,N二甲基甲酰胺、乙酸乙酯、石油醚、己烷、乙醚和四氯化碳中的一种或几种的组合。
优选的,在步骤(1)之前还包括以下步骤:
(a)配制水相:加入含钠盐的水溶液和分散剂,搅拌,得到水相,所述分散剂占水相的重量比为0.1~2.0%;
(b)配制油相:加入第一单体、交联剂、引发剂、和致孔剂,混合,得到油相,所述第一单体和交联剂组成反应物;
(c)制备第一树脂:将步骤(b)中所述油相,加入到步骤(a)所述水相中,搅拌,加 热,温度控制在50~120℃,反应2~10h,然后控制温度在80~150℃,反应2~12h,冷却至室温,抽提,清洗,得到第一树脂。
优选的,步骤(a)所述分散剂为羟乙基纤维素、明胶、聚乙烯醇、活性磷酸钙、古尔胶、甲基纤维素、十二烷基苯磺酸钠和木质素磺酸钠中一种或几种的组合,步骤(a)所述钠盐为磷酸三钠、磷酸氢二钠、磷酸二氢钠和氯化钠中一种或几种的组合,步骤(b)中所述交联剂为乙二醇二乙基二烯丙基酯、乙二醇二甲基丙烯酸酯、二乙烯苯、三烯丙基氰脲酸酯和三羟甲基丙烷三甲基丙烯酸酯中一种或几种的组合;步骤(b)所述致孔剂为环己醇、异丙醇、正丁醇、200#溶剂油、甲苯、二甲苯、乙酸乙酯、正辛烷和异辛烷中一种或几种的组合;步骤(b)所述引发剂为偶氮二异丁腈和过氧化苯甲酰中一种或几种的组合。
优选的,步骤(b)中所述第一单体与所述交联剂摩尔比为1:(0.05~0.3),所述第一单体与所述致孔剂摩尔比在1:(0.1~0.5),所述引发剂重量占油相的总重量的0.5~1.5%。
优选的,所述第一树脂的基本结构为式(301)、式(302)、式(303)和式(304)中的一种或几种的组合,
其中,所述R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为H或烃基,所述m、n、k和p为重复单元的数量,数值范围均为500~3000;
R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13的碳原子数范围均 为0~30;
当R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为烃基时,碳原子数优选为1~30,进一步优选1~20,再进一步优选为5~20,最优选为5~15。
t和q的碳原子数范围为1-30,t和q的碳原子数范围为1-30,进一步优选为1-20,再进一步优选为1-10;
优选的,所述第一单体为式(401)、式(402)、式(403)和式(404)中的一种或几种的组合,
其中,所述R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为H或烃基;
t和q的碳原子数范围为1-30,t和q的碳原子数范围为1-30,进一步优选为1-20,再进一步优选为1-10;
R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13的碳原子数范围均为0~30;
当R
0、R
1、R
2、R
3、R
4、R
5、R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为烃基时,碳原子数优选为1~30,进一步优选1~20,再进一步优选为5~20,最优选为5~15。
本发明还提供了一种复合功能树脂在杀菌中的应用,所述复合功能树脂为上述所得复合功能树脂。
本发明还提供了一种复合功能树脂在水处理中的应用,所述复合功能树脂为上述所得复合功能树脂。
3、有益效果
相比于现有技术,本发明的有益效果为:
(1)本发明的复合功能树脂对水中的病原菌的去除率高,部分情况下可达到99.9%以上,且再生后的树脂仍具有较强的除菌能力,使用寿命长,同时降低了后续消毒负荷,减少消毒剂的使用量,降低运行成本;
(2)本发明的复合功能树脂能有效降低水体环境中含量1000mg/L以下氯离子(或相等当量多种阴离子)或低于3mg/L天然有机物对季铵盐树脂杀菌的拮抗作用,接近去离子水环境中季铵盐树脂杀菌效率,提高了对水体环境中高浓度氯离子等阴离子和高浓度天然有机物的抗干扰能力;
(3)本发明的复合功能树脂同时具有较好的有机物去除率,有效去除尤其是消毒副产物前驱体,以及硝酸盐、磷酸盐等多种阴离子污染物,降低后续采用氯气、臭氧等消毒过程中产生的各类消毒副产物,复合功能树脂沉降性能优良,可以采用流化床装置,实现大水量处理;
(4)本发明还提供了一种复合功能树脂的制备方法,该方法将含有环氧基团第一树脂与第一胺盐进行第一次季铵化,通过控制相关的反应条件及第一胺盐的类型,使得第一次季铵化基本都在第一树脂的外表面进行,然后再与第二胺盐进行第二次季铵化,通过控制相关的反应条件及第二胺盐的类型,使得第二次季铵化基本都在第一树脂的内表面进行,从而得到本发明的复合功能树脂。
图1是本发明一优选的实施例1的树脂A0在不同Cl
-浓度下,对铜绿假单胞菌的杀菌效率;
图2是本发明一优选的实施例2的复合功能树脂A1在不同Cl
-浓度下,对铜绿假单胞菌的杀菌效率;
图3是本发明一优选的实施例1的树脂A0在不同NOM浓度下,对铜绿假单胞菌的杀菌效率;
图4是本发明一优选的实施例2的复合功能树脂A1在不同NOM浓度下,对铜绿假单胞菌的杀菌效率;
图5是本发明一优选的实施例3、一优选的实施例7、一优选的实施例10和一优选的实施例14中,对每个实施例中的第一次季铵化的树脂和第二次季铵化的树脂,分别测定的表面 氮含量和总氮含量,表征特定反应条件调控下第一次季铵化主要发生在树脂表面,第二次季铵化主要发生在树脂内部;
图6是本发明的红外谱图(F T I R),其中1105cm
-1出现季铵化后的C—N伸缩振动吸收峰,a为实施例1的第一树脂的红外图谱,b为实施例1的树脂A0的红外图谱,c为实施例2的复合功能树脂A1的红外图谱。
下面结合附图对本发明进行详细描述。
实施例1
对照组
配制500g水相:称取2.5g羟乙基纤维素,25g硫酸钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在300rpm。称取60g第一单体,本实施例中,第一单体为甲基丙烯酸缩水甘油酯,将60g甲基丙烯酸缩水甘油酯(GMA)、10g二乙烯苯(DVB)、0.6g偶氮二异丁酯、1.8g过氧化苯甲酰、30g环己醇,加入到三口烧瓶中并升温至60℃,反应8h,而后升温至90℃,反应4h;冷却至室温,收取白色或类白色丙烯酸树脂球,抽提、清洗后晾干,丙烯酸树脂即为第一树脂。
合成并分选丙烯酸树脂(平均粒径500um),称取第一胺盐80g,本实施例中,第一胺盐为十二烷基二甲胺盐酸盐,将20g第一树脂和80g十二烷基二甲胺盐酸盐置于250mL的三口瓶中,控温60℃,搅拌200rpm,溶剂为甲醇,乙醇,甲醇/乙醇体积比为3:7,回凝反应24h,冷却过滤,索氏抽提(用甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到第一次季铵化的树脂,测定其强碱交换量为1.51mmol/g,树脂表面电荷密度约为1.98*10
23N
+/g,树脂表面N含量占树脂总N含量21.8%,第一次季铵化树脂的产品编号为A0。
本实施例得到的树脂A0杀菌性能评定如下:
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L、1000mg/L、3000mg/L和9000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,加入0.5g的树脂A0,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算杀菌效率。评定结果如图1所示,在氯离子含量为0mg/L、100mg/L、1000mg/L、3000mg/L和9000mg/L时,对应的杀菌效率分别为99.99%、96.20%、52.35%、22.55%和13.30%。
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、1mg/L、3mg/L、5mg/L和10mg/L浓度NOM稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,加入0.5g的树脂A0,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl 进行平板涂布计数,计算杀菌效率。评定结果如图3所示,在NOM浓度分别为0mg/L、1mg/L、3mg/L、5mg/L和10mg/L时,对应的杀菌效率分别为99.93%、99.82%、63.53%、35.29%和13.52%。
如图6所示,a为本实施例的第一树脂的红外图谱,b为本实施例的树脂A0的红外图谱;
NOM(natural organicmatter,简称NOM),主要指油脂、糖类、蛋白质、天然橡胶这些自然界分布广泛的有机物,由于这类物质都是在生物体内合成的有机化合物,因此称为天然有机物。
实施例2
配制500g水相:称取2.5g羟乙基纤维素,25g硫酸钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在300rpm。称取60g第一单体,本实施例中,第一单体为甲基丙烯酸缩水甘油酯,将60g甲基丙烯酸缩水甘油酯(GMA)、10g二乙烯苯(DVB)、0.6g偶氮二异丁酯、1.8g过氧化苯甲酰、30g环己醇,加入到三口烧瓶中并升温至60℃,反应8h,而后升温至90℃,反应4h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,即得到第一树脂。
合成并分选第一树脂(平均粒径500um),称取第一胺盐80g,本实施例中,第一胺盐为十二烷基二甲胺盐酸盐,将20g第一树脂和80g十二烷基二甲胺盐酸盐置于250mL的三口瓶中,控温60℃,搅拌400rpm,溶剂为甲醇,乙醇,甲醇/乙醇体积比为3:7,回凝反应24h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为A1-1,共21.05g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐,本实施例中第二胺盐为三乙胺盐酸盐,加入三乙胺盐酸盐60g,溶剂为40%乙醇,控温70℃,搅拌250rpm,回凝反应30h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.15mmol/g,复合功能树脂表面电荷密度约为2.08*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量16.1%,复合功能树脂的产品编号为A1,共22.50g。
本实施例中复合功能树脂的重复单元数范围为2700-3000;
如图6所示,c为本实施例的复合功能树脂A1的红外图谱。
本实施例得到的复合功能树脂A1杀菌性能评定如下:
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L、1000mg/L、3000mg/L和9000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,加入0.5g的树脂A1,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算杀菌效率。评定结果如图2所示,在氯离子含量为0mg/L、 100mg/L、1000mg/L、3000mg/L和9000mg/L时,对应的杀菌效率分别为99.99%、99.95%、99.81%、85.45%和50.55%。
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、1mg/L、3mg/L、5mg/L和10mg/L浓度NOM稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,加入0.5g的树脂A1,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算杀菌效率。评定结果如图4所示,在NOM浓度分别为0mg/L、1mg/L、3mg/L、5mg/L和10mg/L时,对应的杀菌效率分别为99.99%、99.94%、99.88%、80.60%和39.19%。
实施例3
本实施例的第一单体选自式(401),当R
0为H,R
1为-CH
3,t=1时,第一单体结构为式(401-1),
具体实施如下:
配制500g水相:称取2.5g甲基纤维素,5g十二烷基苯磺酸钠,50g硫酸钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在400rpm。将40g式(401-1)所示的第一单体、20g丙烯酸甲酯(MA)、20g苯乙烯、5g乙二醇二甲基丙烯酸酯、10g三羟甲基丙烷三甲基丙烯酸酯、1.0g偶氮二异丁酯、10g 200#溶剂油、10g正丁醇,加入到三口烧瓶中并升温至50℃,反应12h,而后升温至80℃,反应4h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,即得到第一树脂。
合成并分选第一树脂(平均粒径500um),称取第一胺盐80g,本实施例中,第一胺盐为N,N-二甲基辛胺盐酸盐,将20g第一树脂和120g N,N-二甲基辛胺盐酸盐置于250mL的三口瓶中,控温70℃,搅拌300rpm,溶剂为N,N二甲基甲酰胺,回凝反应30h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为A2-1,共21.30g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐,本实施例中第二胺盐为三甲胺盐酸盐,加入三甲胺盐酸盐50g,溶剂为乙腈,控温70℃,搅拌300rpm,回凝反应24h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.25mmol/g,复合功能树脂表面电荷密度约为 2.72*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量20.0%,复合功能树脂的产品编号为A2,共21.80g。
本实施例中复合功能树脂的重复单元数范围为2500-2700;
如图5所示,对第一次季铵化的树脂A2-1测定其表面氮含量,总氮含量,对复合功能树脂A2测定其表面氮含量,总氮含量,得到图5,由此可知,本实施例的第一次季铵化主要发生在树脂表面,第二次季铵化主要发生在树脂内部。
实施例4
本实施例的第一单体选自式(401),当R
0为-CH
2CH
3,R
1为-CH
3,t=2时,第一单体结构为式(401-2),
第一胺盐选自式(205),当X
-为Cl
-时,第一胺盐为式(205-1);
第二胺盐选自式(201),当X
-为Cl
-时,第二胺盐为式(201-1);
具体实施如下:
配制500g水相:称取2.5g明胶,2.5g古尔胶,50g硫酸钠,50g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在280rpm。将50g的式(401-2)所示第一单体、20g丙烯酸丁酯、10g MA、1g乙二醇二甲基丙烯酸酯、1.5g过氧化苯甲酰、10g 甲苯、15g二甲苯、10g正辛烷,加入到三口烧瓶中并升温至105℃,反应12h,而后升温至130℃,反应4h;冷却至室温,收取白色或类白色丙烯酸树脂球,抽提、清洗后晾干,丙烯酸树脂即为第一树脂。
合成并分选第一树脂(粒径10um),将20g的第一树脂和100g的第一胺盐置于250mL的三口瓶中,本实施例中第一胺盐为式(205-1)所示化合物,控温85℃,搅拌400rpm,溶剂为甲苯,回凝反应24h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为A3-1,共20.85g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐50g,第二胺盐为式(201-1)所示化合物,溶剂为乙烷,控温60℃,搅拌480rpm,回凝反应40h,冷却过滤,索氏抽提(用甲醇、乙醇、丙酮),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为0.33mmol/g,复合功能树脂表面电荷密度约为2.01*10
19N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量10.12%,复合功能树脂的产品编号为A3,共21.50g。
当复合功能树脂A3的X
-为Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-和CO
3
2-之中任意一种时,也能取得类似效果。
本实施例中复合功能树脂的重复单元数范围为2000-2500;
实施例5
本实施例的第一单体选自式(403),当R
2为-H,R
3为-CH
3,R
4为-H,R
5为-H时,第一单体结构为式(403-1),
本实施例中第一胺盐选自式(208)所示化合物,当X为I
-时,第一胺盐为式(208-1)
本实施例中第二胺盐选自式(202),当R
14为-CH
3,X
-为Cl
-时,第二胺盐为(202-2)
具体实施如下:
配制500g水相:称取2.5g聚乙烯醇,15g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在200rpm。将45g的式(403-1)所示第一单体、35g二乙烯苯(DVB)、5g甲苯、5g正庚烷、5g环己醇、0.5g偶氮二异丁酯(AIBN),加入到三口烧瓶中并升温至55℃,反应12h,而后升温至75℃,反应12h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,得到第一树脂。
合成并分选的第一树脂(平均粒径2000um),将20g第一树脂和80g的式(208-1)所示化合物置于250mL的三口瓶中,控温70℃,搅拌250rpm,溶剂为四氯化碳,回凝反应10h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为B1-1,共20.90g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入式(202-2)所示化合物80g,溶剂为乙酸乙酯,控温65℃,搅拌300rpm,回凝反应40h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为0.3073mmol/g,复合功能树脂表面电荷密度约为9.01*10
15N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量0.005%,复合功能树脂的产品编号为B1,共21.59g。
本实施例中复合功能树脂的重复单元数范围为1500-2000。
实施例6
本实施例的第一单体由两种不同的第一单体组成,
第一种第一单体选自式(403),当R
2为-CH
3,R
3为-CH
3,R
4为-H,R
5为-H时,第一种第一单体结构为式(403-2),
第二种第一单体为甲基丙烯酸缩水甘油酯(GMA);
本实施例中第一胺盐为N,N'-二苄基乙二胺盐酸盐;
本实施例中第二胺盐选自式(203),当X
-为Cl
-时,第二胺盐为式(203-1)
具体实施如下:
配制500g水相:称取2.5g聚乙烯醇,1.5g羟乙基纤维素,25g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在300rpm。将40g式(403-2)所示化合物、20g甲基丙烯酸缩水甘油酯(GMA)、15.0g二乙烯苯(DVB)、10g甲苯、10g二甲苯、10g环己醇、0.5g过氧化苯甲酰、0.25g偶氮二异丁酯,加入到三口烧瓶中并升温至65℃,反应12h,而后升温至75℃,反应8h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,得到第一树脂。
合成并分选第一树脂(平均粒径100um),将20g第一树脂和50g N,N'-二苄基乙二胺盐酸盐置于250mL的三口瓶中,控温110℃,搅拌280rpm,溶剂为甲苯,回凝反应24h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为B2-1,共21.51g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐80g,溶剂为乙醇,控温70℃,搅拌380rpm,回凝反应30h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.46mmol/g,复合功能树脂表面电荷密度约为1.39*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量15.8%,复合功能树脂的产品编号为B2,共22.19g。
本实施例中复合功能树脂的重复单元数范围为2000-2300;
当复合功能树脂B2的X
-为Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-和CO
3
2-之中任意一种时,也能取得类似效果。
实施例7
本实施例的第一单体选自式(403),当R
2为-H,R
3为-CH
3,R
4为-CH
2CH
3,R
5为-H时,第一单体结构为式(403-3),
本实施例中第一胺盐为N,N-二甲基正辛胺盐酸盐,本实施例中第二胺盐为三甲胺盐酸盐;
具体实施如下:
配制500g水相:称取2.5g甲基纤维素,2.5g羟乙基纤维素,25g硫酸钠,25g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在250rpm。将40g式(403-3)所示化合物、10g丙烯酸甲酯(MA)、5g丙烯酸丁酯、10g乙二醇二甲基丙烯酸酯、10g乙二醇二甲基丙烯酸酯、10g 200#溶剂油、10g正丁醇、5g环己醇、1.0g偶氮二异丁酯,加入到三口烧瓶中并升温至80℃,反应12h,而后升温至90℃,反应8h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,得到第一树脂。
合成并分选第一树脂(平均粒径500um),将20g第一树脂和100g N,N-二甲基正辛胺盐酸盐置于250mL的三口瓶中,控温60℃,搅拌380rpm,溶剂为乙醇,回凝反应40h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为B3-1,共21.35g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三甲胺盐酸盐60g,溶剂为甲醇,控温70℃,搅拌300rpm,回凝反应24h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.12mmol/g,复合功能树脂表面电荷密度约为2.44*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量19.1%,复合功能树脂的产品编号为B3,共22.90g。
本实施例中复合功能树脂的重复单元数范围为500-1000;
如图5所示,对第一次季铵化的树脂B3-1测定其表面氮含量,总氮含量,对复合功能树脂B3测定其表面氮含量,总氮含量,得到图5,由此可知,本实施例的第一次季铵化主要发生在树脂表面,第二次季铵化主要发生在树脂内部。
实施例8
本实施例的第一单体由两种不同的第一单体组成,
第一种第一单体选自式(403),当R
2为-H,R
3为-CH
3,R
4为-H,R
5为-H时,第一种第一单体结构为式(403-1),
第二种第一单体为甲基丙烯酸缩水甘油酯(GMA);
本实施例中第一胺盐为双十八烷基甲基胺盐酸盐,本实施例中第二胺盐为三甲胺盐酸盐;
具体实施如下:
配制500g水相:称取1.25g古尔胶,1.25g木质素磺酸钠,25g硫酸钠,15g碳酸氢钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在280rpm。将30g式(403-1)所示化合物、10g GMA、10g MA、10g三羟甲基丙烷三甲基丙烯酸、10g三烯丙基氰脲酸酯、10g 200#溶剂油、5g异辛烷、5g异丙醇、1.5g过氧化苯甲酰,加入到三口烧瓶中并升温至70℃,反应12h,而后升温至95℃,反应8h;冷却至室温,收取白色或类白色树脂球,抽提、清洗后晾干,得到第一树脂。
合成并分选第一树脂(平均粒径10um),将20g第一树脂和100g四甲基乙二胺盐酸盐置于250mL的三口瓶中,控温120℃,搅拌340rpm,溶剂为N,N二甲基甲酰胺,回凝反应40h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为B4-1,共21.20g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三甲胺盐酸盐80g,溶剂为四氯化碳,控温70℃,搅拌300rpm,回凝反应40h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为3.99mmol/g,复合功能树脂表面电荷密度约为1.20*10
24N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量49.87%,复合功能树脂的产品编号为B4,共22.75g。
本实施例中复合功能树脂的重复单元数范围为1200-1800。
实施例9
本实施例的第一单体选自式(402),当q=1时,第一单体结构为式(402-1),
本实施例中第一胺盐为十六烷基二甲基胺盐,本实施例中第二胺盐为三丙胺盐酸盐;
具体实施如下:
配制500g水相:称取2.5g聚乙烯醇,5g碳酸氢铵,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在250rpm。将100g第一单体、8g双甲基丙烯酸乙二醇酯(EGDM)、40g甲苯、0.5g偶氮二异丁腈、0.5g过氧化二碳酸二环己酯、硬脂肪酸钙2g、20g白油,加入到三口烧瓶中并升温至60℃,反应10h,而后升温至80℃,反应6h;冷却至室温,提取甲苯,白油,烘干收袋,得到第一树脂。
合成并分选第一树脂(平均粒径100um),将20g第一树脂和80g十六烷基二甲基胺盐置于250mL的三口瓶中,控温100℃,搅拌280rpm,溶剂为甲苯,回凝反应30h,冷却至室温, 过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为C1-1,共21.80g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三丙胺盐酸盐80g,溶剂为四氯化碳,控温70℃,搅拌300rpm,回凝反应40h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.90mmol/g,复合功能树脂表面电荷密度约为2.16*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量18.9%,复合功能树脂的产品编号为C1,共22.55g。
本实施例中复合功能树脂的重复单元数范围为1000-1600。
实施例10
本实施例的第一单体由两种不同的第一单体组成,
第一种第一单体选自式(402),当q=2时,第一种第一单体结构为式(402-2),
第二种第一单体为甲基丙烯酸缩水甘油酯(GMA);
本实施例中第一胺盐为N,N-二甲基己胺盐酸盐,本实施例中第二胺盐为三甲胺盐酸盐;
具体实施如下:
配制500g水相:称取1.5g聚乙烯醇,1.5g羟乙基纤维素,5g碳酸氢铵,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在350rpm。将80g式(402-2)所示化合物、20g GMA、10g三烯丙基异氰脲酸酯、20g甲苯、10g二甲苯、0.5g过氧化二碳酸二环己酯、0.5g偶氮二异丁腈、硬脂肪酸锌2g、30g白油,加入到三口烧瓶中并升温至56℃,反应10h,而后升温至75℃,反应8h;冷却至室温,提取甲苯、二甲苯,白油,烘干收袋,得到第一树脂。
合成并分选第一树脂(平均粒径500um),将20g第一树脂和40g N,N-二甲基己胺盐酸盐置于250mL的三口瓶中,控温70℃,搅拌450rpm,溶剂为乙醇,回凝反应20h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为C2-1,共21.89g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三甲胺盐酸盐70g,溶剂为甲醇,控温70℃,搅拌300rpm,回凝反应24h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.35mmol/g,复合功能树脂表面电荷密度约为3.04*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量21.5%,复合功能树脂的产品编号为C2,共23.05g。
如图5所示,对第一次季铵化的树脂C2-1测定其表面氮含量,总氮含量,对复合功能树 脂C2测定其表面氮含量,总氮含量,得到图5,由此可知,本实施例的第一次季铵化主要发生在树脂表面,第二次季铵化主要发生在树脂内部。
实施例11
本实施例的第一单体由两种不同的第一单体组成,
第一种第一单体选自式(402),当q=3时,第一种第一单体结构为式(402-3),
第二种第一单体为甲基丙烯酸缩水甘油酯(GMA);
本实施例中第一胺盐选自式(206),当R
14为-H时,X为Cl
-时,第一胺盐为式(206-1)
本实施例中第二胺盐选自式(202),当R
14为-H时,X为Cl
-时,第二胺盐为式(202-1)
具体实施如下:
配制500g水相:称取2.5g古尔胶,5g十二烷基苯磺酸钠,5g碳酸氢铵,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在280rpm。将60g式(402-3)所示化合物、30g GMA、10g MA、13g N,N-亚甲基双丙烯酰胺、20g的200#溶剂油、10g正丁醇、0.5g过氧化苯甲酰、0.3g偶氮二异丁腈、癸二酸钙2g、15g白油,加入到三口烧瓶中并升温至65℃,反应10h,而后升温至90℃,反应6h;冷却至室温,提取200#溶剂油、正丁醇,白油,烘干收袋,得到第一树脂。
合成并分选第一树脂(平均粒径200um),将20g第一树脂和100g第一胺盐置于250mL的三口瓶中,控温120℃,搅拌350rpm,溶剂为N,N二甲基甲酰胺,回凝反应30h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为C3-1,共21.15g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐40g,溶剂为乙酸乙酯,控温70℃,搅拌300rpm,回凝反应40h,冷却过滤,索氏抽提(甲醇、乙 醇和丙酮之一或组合都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.68mmol/g,复合功能树脂表面电荷密度约为1.71*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量16.9%,产品编号为C3,共21.85g。
当第一胺盐、第二胺盐的X
-为Br
-、I
-、I3
-、I5
-、I7
-、OH
-、SO
4
2-、HCO
3
-和CO
3
2-之中任意一种时,也能取得类似效果。
实施例12
本实施例的第一单体由两种不同的第一单体组成,
第一种第一单体选自式(402),当q=4时,第一种第一单体结构为式(402-4),
第二种第一单体为甲基丙烯酸缩水甘油酯(GMA);
本实施例中第一胺盐选自式(204),当R
14为-H时,X为Cl
-时,第一胺盐为式(204-1)
本实施例中第二胺盐为三乙胺盐酸盐;
具体实施如下:
配制500g水相:称取2.5g古尔胶,1.5g活性磷酸钙,7.5g碳酸氢铵,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在450rpm。将60g式(402-4)所示化合物、20g GMA、20g丙烯酸甲酯、20g丙烯酸丁酯、13g N,N-亚甲基双丙烯酰胺、5g双甲基丙烯酸乙二醇酯、15g异辛烷、10g正辛烷、0.5g过氧化苯甲酰、0.5g过氧化二碳酸二环己酯、月桂酸钙2g、25g白油,加入到三口烧瓶中并升温至80℃,反应10h,而后升温至110℃,反应12h;冷却至室温,提取异辛烷、正辛烷,白油,烘干收袋,得到第一树脂。
合成并分选第一树脂(平均粒径600um),将20g第一树脂和100g式(204-1)所示化合物置于250mL的三口瓶中,控温70℃,搅拌250rpm,溶剂为甲苯,回凝反应24h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为C4-1,共20.85g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三乙胺盐酸盐60g,溶剂为甲醇,控温70℃,搅拌250rpm,回凝反应30h,冷却过滤,索氏抽提(甲醇、乙醇和丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.87 mmol/g,复合功能树脂表面电荷密度约为2.13*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量18.9%,复合功能树脂的产品编号为C4,共21.60g。
实施例13
本实施例的第一单体选自式(404),当R
6、R
7、R
8、R
9、R
10、R
11、R
12和R
13为H时,第一单体的结构式为式(404-1)
第一胺盐为十二烷基二甲胺盐酸盐,第二胺盐为三甲胺盐酸盐;
配制500g水相:称取5g古尔胶,10g活性磷酸钙,7.5g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在300rpm,保持通氮气除氧。将60g式(404-1)所示化合物、30g二乙烯苯、30g 200#汽油、0.5g过氧化苯甲酰、1.0g偶氮二异丁腈,通氮气除氧10min后,加入到三口烧瓶中,保持通氮气,室温搅拌10min后,升温至50℃聚合温度,反应2h,而后升温至80℃,反应2h;冷却至室温,清洗,抽提、晾干,得到第一树脂。
合成并分选第一树脂(平均粒径20um),将20g第一树脂和60g十二烷基二甲胺盐酸盐置于250mL的三口瓶中,控温75℃,搅拌300rpm,溶剂为乙醇,回凝反应35h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为D1-1,共21.35g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入第二胺盐三甲胺盐酸盐50g,溶剂为甲醇,控温70℃,搅拌300rpm,回凝反应24h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.08mmol/g,复合功能树脂表面电荷密度约为2.42*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量19.3%,复合功能树脂的产品编号为D1,共22.18g。
实施例14
本实施例的第一单体选自式(404),当R
6、R
8、R
9、R
10、R
11、R
12和R
13为H,R
7为-CH
3时,第一单体的结构式为式(404-2)
第一胺盐为N,N-二甲基己胺盐酸盐,第二胺盐为三乙胺盐酸盐;
配制500g水相:称取2.5g羟乙基纤维素,1.5g甲基纤维素,15g硫酸钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在220rpm,保持通氮气除氧。将71.1g式(404-2)所示化合物、67.5g二乙烯苯、82.8g甲苯、24.6g过氧化苯甲酰,通氮气除氧10min后,加入到三口烧瓶中,保持通氮气,室温搅拌10min后,升温至85℃聚合温度,反应6h,而后升温至115℃,反应7h;冷却至室温,清洗,抽提、晾干,得到第一树脂。
合成并分选第一树脂(平均粒径400um),将20g第一树脂和10g N,N-二甲基己胺盐酸盐置于250mL的三口瓶中,控温50℃,搅拌200rpm,溶剂为甲苯,回凝反应12h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为D2-1,共21.75g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三乙胺盐酸盐10.9g,溶剂为四氯化碳,控温150℃,搅拌800rpm,回凝反应72h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为2.39mmol/g,复合功能树脂表面电荷密度约为3.00*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量20.8%,复合功能树脂的产品编号为D2,共22.43g。
如图5所示,对第一次季铵化的树脂D2-1测定其表面氮含量,总氮含量,对复合功能树脂D2测定其表面氮含量,总氮含量,得到图5,由此可知,本实施例的第一次季铵化主要发生在树脂表面,第二次季铵化主要发生在树脂内部。
在本实施例中,羟乙基纤维素和甲基纤维素也可以用明胶、聚乙烯醇、活性磷酸钙、古尔胶、十二烷基苯磺酸钠和木质素磺酸钠中一个或组合代替,也能够实现相应的反应。
在本实施例中,硫酸钠用磷酸三钠、磷酸氢二钠、磷酸二氢钠和氯化钠中一种或几种的组合代替也能实现相应的反应。
在本实施例中,二乙烯苯用乙二醇二乙基二烯丙基酯、乙二醇二甲基丙烯酸酯、三烯丙基氰脲酸酯和三羟甲基丙烷三甲基丙烯酸酯中一种或几种的组合代替也能实现相应的反应。
在本实施例中,环己醇用异丙醇、正丁醇、200#溶剂油、甲苯、二甲苯、乙酸乙酯、正辛烷和异辛烷中一种或几种的组合也能实现相应的反应。
实施例15
当R
6、R
8、R
9、R
10、R
11、R
12和R
13为H,R
7为-CH
3时,结构式为式(404-2)
本实施例的第一单体由式(404-2)所示化合物组成;
第一胺盐为式(208-1)所示化合物,第二胺盐为三丙胺盐酸盐;
配制500g水相:称取2.5g木质素磺酸钠,5g十二烷基苯磺酸钠,25g硫酸钠,25g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在380rpm,保持通氮气除氧。将71.1g式(404-2)所示化合物、117g二乙烯苯、138g甲苯、5.1g过氧化苯甲酰,通氮气除氧10min后,加入到三口烧瓶中,保持通氮气,室温搅拌10min后,升温至120℃聚合温度,反应10h,而后升温至150℃,反应12h;冷却至室温,清洗,抽提、晾干,得到第一树脂。
合成并分选的吡啶第一树脂(平均粒径10um),将20g第一树脂和100g式(208-1)所示化合物置于250mL的三口瓶中,控温150℃,搅拌800rpm,溶剂为N,N二甲基甲酰胺,回凝反应72h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为D3-1,共21.03g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入三丙胺盐酸盐105g,溶剂为甲醇,控温50℃,搅拌200rpm,回凝反应12h,冷却过滤,索氏抽提(甲醇、乙醇、丙酮都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.82mmol/g,复合功能树脂表面电荷密度约为1.91*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量17.4%,复合功能树脂的产品编号为D3,共21.90g。
本实施例中复合功能树脂的重复单元数范围为500-800。
实施例16
当R
6、R
8、R
9、R
10、R
11、R
12和R
13为H,R
7为-CH
3时,结构式为式(404-2)
本实施例的第一单体为式(404-2)所示化合物;
第一胺盐为双十八烷基甲基胺盐酸盐;
第二胺盐为式(202-2)所示化合物;
配制500g水相:称取5g明胶,1g活性磷酸钙,7.5g氯化钠,其余为水;
将500g水相加入2L三口烧瓶中,搅拌转速控制在200rpm,保持通氮气除氧。将71.1g式(404-2)所示化合物、19.5g二乙烯苯、27.6g甲苯、0.6g过氧化苯甲酰,通氮气除氧10min后,加入到三口烧瓶中,保持通氮气,室温搅拌10min后,升温至90℃聚合温度,反应10h,而后升温至120℃,反应4h;冷却至室温,清洗,抽提、晾干,得到第一树脂。
合成并分选第一树脂(平均粒径300um),将20g第一树脂和200g双十八烷基甲基胺盐酸盐置于250mL的三口瓶中,控温100℃,搅拌501rpm,溶剂为甲苯,回凝反应40h,冷却至室温,过滤,无水乙醇、去离子水各漂洗2次,得到第一次季铵化的树脂,编号为D4-1,共21.28g;将上述第一次季铵化的树脂加入洗净的250mL的三口瓶中,加入式(202-2)所示化合物210.3g,溶剂为乙醇,控温100℃,搅拌497rpm,回凝反应40h,冷却过滤,索氏抽提(甲醇、乙醇和丙酮之一或组合都可以),去离子水充分漂洗,得到本发明的复合功能树脂,测定其强碱交换量为1.95mmol/g,复合功能树脂表面电荷密度约为1.87*10
23N
+/g,复合功能树脂表面N含量占复合功能树脂总N含量15.9%,复合功能树脂的产品编号为D4,共22.35g。
实施例17
本实施例为季铵盐树脂杀菌性能评定
选用大肠杆菌ATCC 8099,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl-稀释至10
5CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例1得到的树脂A0和实施例2得到树脂A1各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表1不同季铵盐树脂对大肠杆菌的去除效果
注:A0~对照组(仅十二烷基二甲基叔胺季铵化);A1~实验组(十二烷基二甲胺盐酸盐+三乙胺盐酸盐季铵化)。
实施例18
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别实施例1得到的树脂A0和实施例2得到树脂A1各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表2不同季铵盐树脂对铜绿假单胞菌的去除效果
注:A0—对照组(仅十二烷基二甲基叔胺季铵化);A1—实验组(十二烷基二甲胺盐酸盐+三乙胺盐酸盐季铵化)
实施例19
本实施例为季铵盐树脂杀菌性能评定
选用大肠杆菌ATCC 8099,营养肉汤培养后,以0mg/L、1mg/L、3mg/L和5mg/L的NOM(天然有机物)稀释至10
5CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例1得到的树脂A0和实施例2得到树脂A1各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表3不同季铵盐树脂对大肠杆菌的去除效果
注:A0—对照组(仅十二烷基二甲基叔胺季铵化);A1—实验组(十二烷基二甲胺盐酸盐+三乙胺盐酸盐季铵化)
实施例20
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、1mg/L、3mg/L和5mg/L浓度NOM稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例1得到的树脂A0和实施例2得到树脂A1各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表4不同季铵盐树脂对铜绿假单胞菌的去除效果
注:A0—对照组(仅十二烷基二甲基叔胺季铵化);A1—实验组(十二烷基二甲胺盐酸盐 +三乙胺盐酸盐季铵化)
实施例21
本实施例为季铵盐树脂杀菌性能和污染物去除性能评定
将实验菌液替换成实际水体,水质参数如下:TOC为2.10mg/L,NO
3
-为0.41mg/L,Cl
-为68mg/L,SO
4
2-为55mg/L,取实际水体10L,分别加入实施例1得到的树脂A0和实施例2得到树脂A1各50g,然后置于搅拌下,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表5不同季铵盐树脂对实际水体细菌总数去除效果
表6不同季铵盐树脂对实际水体的TOC去除效果
实施例22
本实施例为季铵盐树脂对实际饮用水中病原菌和污染物去除效果评价
选取某自来水厂砂滤出水,水质参数如下:TOC为3.30mg/L,NO
3
-为1.52mg/L,Cl
-为48mg/L,SO
4
2-为27mg/L,取实际水体10L,而后分别加入实施例1得到的树脂A0和实施例2得到树脂A1各50g,然后置于搅拌下,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表7不同季铵盐树脂对实际水体细菌总数去除效果
表8不同季铵盐树脂对实际水体中大肠杆菌去除效果
表9不同季铵盐树脂对实际水体中铜绿假单胞菌去除效果
表10不同季铵盐树脂对实际水体的TOC去除效果
实施例23
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例7合成的树脂B3各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表11不同季铵盐树脂对铜绿假单胞菌的去除效果
实施例24
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例10合成的树脂C2各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表12不同季铵盐树脂对铜绿假单胞菌的去除效果
实施例25
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例12合成的树脂C4各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表13不同季铵盐树脂对铜绿假单胞菌的去除效果
实施例26
本实施例为季铵盐树脂杀菌性能评定
选用铜绿假单胞菌ATCC 15442,营养肉汤培养后,以0mg/L、100mg/L和1000mg/L浓度Cl
-稀释至10
6CFU/mL菌落数;取100mL配制的实验菌液至250mL锥形瓶中,分别加入实施例15合成的树脂D3各0.5g,然后置于摇床中,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表14不同季铵盐树脂对铜绿假单胞菌的去除效果
实施例27
本实施例为季铵盐树脂杀菌性能评定
本实施例为季铵盐树脂对实际饮用水中病原菌和污染物去除效果评价
选取某自来水厂砂滤出水,水质参数如下:TOC为2.85mg/L,NO
3
-为1.38mg/L,Cl
-为65mg/L,SO
4
2-为34mg/L,取实际水体10L,而后分别加入实施例3、实施例7、实施例10和实施例14合成的树脂A2、B3、C2和D2各50g,然后置于搅拌下,200rpm,20±1℃,60min;最后分别取100μl进行平板涂布计数,计算各季铵盐杀菌效率。评定结果统计入下表:
表15不同季铵盐树脂对实际水体细菌总数去除效果
表16不同季铵盐树脂对实际水体中大肠杆菌去除效果
表17不同季铵盐树脂对实际水体中铜绿假单胞菌去除效果
表18不同季铵盐树脂对实际水体的TOC去除效果
Claims (19)
- 根据权利要求1所述的复合功能树脂,其特征在于:所述复合功能树脂的交联度为1~35%,所述复合功能树脂的为粒径10~2000μm,复合功能树脂表面N含量占所述复合功能树脂总N含量0.005~50.0%。
- 根据权利要求1所述的复合功能树脂,其特征在于:所述复合功能树脂的交联度为10~25%,所述复合功能树脂的为粒径为20~600μm,所述复合功能树脂的强碱交换量为0.3~4.0mmol/g,所述复合功能树脂的树脂表面电荷密度为10 15~10 24N +/g。
- 一种复合功能树脂的制备方法,包括以下步骤:(1)加入第一树脂、第一胺盐和溶剂C,搅拌,进行反应,进行第一次季铵化,得到第一次季铵化的树脂;(2)加入步骤(1)所述的第一次季铵化的树脂、第二胺盐和溶剂D,搅拌,进行反应,进行第二次季铵化,得到所述复合功能树脂。
- 根据权利要求5所述的复合功能树脂的制备方法,其特征在于:步骤(1)中所述第一树脂重量与所述第一胺盐的重量比为1:(0.5~10)。
- 根据权利要求6所述的复合功能树脂的制备方法,其特征在于:步骤(1)中反应条件为:反应时间为12~72h,搅拌速度为200~800rpm,反应温度为50~150℃。
- 根据权利要求5所述的复合功能树脂的制备方法,其特征在于:步骤(2)所述第一次季铵化的树脂的重量与所述第二胺盐的重量比为1:(0.5~10)。
- 根据权利要求5所述的复合功能树脂的制备方法,其特征在于:步骤(2)中反应条件为:反应时间为12~72h,搅拌速度为200~800rpm,反应温度为50~150℃。
- 根据权利要求5所述的复合功能树脂的制备方法,其特征在于,所述溶剂C为水、甲醇、乙醇、丙酮、乙腈、苯、甲苯、四氢呋喃、二氯甲烷、N,N二甲基甲酰胺、乙酸乙酯、石油醚、己烷、乙醚和四氯化碳中的一种或几种的组合,所述溶剂D为水、甲醇、乙醇、丙酮、乙腈、苯、甲苯、四氢呋喃、二氯甲烷、N,N二甲基甲酰胺、乙酸乙酯、石油醚、己烷、乙醚和四氯化碳中的一种或几种的组合。
- 根据权利要求5所述的复合功能树脂的制备方法,其特征在于:在步骤(1)之前还包括以下步骤:(a)配制水相:加入含钠盐的水溶液和分散剂,搅拌,得到水相,所述分散剂占水相的重量比为0.1~2.0%;(b)配制油相:加入第一单体、交联剂、引发剂、和致孔剂,混合,得到油相,所述第一单体和交联剂组成反应物;(c)制备第一树脂:将步骤(b)中所述油相,加入到步骤(a)所述水相中,搅拌,加热,温度控制在50~120℃,反应2~10h,然后控制温度在80~150℃,反应2~12h,冷却至室温,抽提,清洗,得到第一树脂。
- 根据权利要求13所述的复合功能树脂的制备方法,其特征在于:步骤(a)所述分散剂为羟乙基纤维素、明胶、聚乙烯醇、活性磷酸钙、古尔胶、甲基纤维素、十二烷基苯磺酸钠和木质素磺酸钠中一种或几种的组合,步骤(a)所述钠盐为磷酸三钠、磷酸氢二钠、磷酸二氢钠和氯化钠中一种或几种的组合,步骤(b)中所述交联剂为乙二醇二乙基二烯丙基酯、乙二醇二甲基丙烯酸酯、二乙烯苯、三烯丙基氰脲酸酯和三羟甲基丙烷三甲基丙烯酸酯中一种或几种的组合;步骤(b)所述致孔剂为环己醇、异丙醇、正丁醇、200#溶剂油、甲苯、二甲苯、乙酸乙酯、正辛烷和异辛烷中一种或几种的组合;步骤(b)所述引发剂为偶氮二异丁腈和过氧化苯甲酰中一种或几种的组合。
- 根据权利要求13所述的复合功能树脂的制备方法,其特征在于:步骤(b)中所述第一单体与所述交联剂摩尔比为1:(0.05~0.3),所述第一单体与所述致孔剂摩尔比在1:(0.1~0.5),所述引发剂重量占油相的总重量的0.5~1.5%。
- 一种复合功能树脂在杀菌中的应用,其特征在于:所述复合功能树脂为权利要求1-17任一项所得复合功能树脂。
- 一种复合功能树脂在水处理中的应用,其特征在于:所述复合功能树脂为权利要求1-18任一项所得复合功能树脂。
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WO2022259872A1 (ja) * | 2021-06-10 | 2022-12-15 | 綜研化学株式会社 | 重合体粒子およびその製造方法 |
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US20210238318A1 (en) | 2021-08-05 |
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